Ukraine has moved towards joining Nato, angering Russia at a time when the Kremlin already views its eastward expansion as a security threat.
Parliament voted overwhelmingly to renounce the country’s “non-aligned” status on Tuesday, which maintained a neutral military and political status.
Speaking before the ballot, Ukrainian Foreign Minister Pavlo Klimkin said the decision underscored the country's increasing co-operation with Europe and the West.
“This will lead to integration in the European and the Euro-Atlantic space,” he said.
But his Russian counterpart, Sergei Lavrov, called the step “counterproductive” and said it would provoke tension in war-torn eastern Ukraine.
“It will only escalate the confrontation and creates the illusion that it is possible to resolve Ukraine's deep internal crisis by passing such laws,” Mr Lavrov said, according to the TASS news agency.
Although Ukraine pursued Nato membership several years ago, it declared itself a non-bloc country after Russia-friendly Viktor Yanukovych became president in 2010.
The latest vote comes as conflict continues between pro-Russian rebels and the Ukrainian government in eastern Ukraine, despite a truce signed in September.
The amendment, proposed by President Petro Poroshenko, passed easily with 303 votes to nine - 77 more than the minimum required to pass into law.
Kiev first announced its intention of seeking the protection of Nato membership in August, following Russia’s suspected involvement in the Ukrainian crisis.
Nato – short for the North Atlantic Treaty Organisation – was founded by Britain, the US, France and other allies at the start of the Cold War and has expanded gradually to include 28 members
Accession to the alliance is likely to take years, but a Nato spokesperson in Brussels said the “door is open”.
“Ukraine will become a member of Nato if it so requests and fulfils the standards and adheres to the necessary principles,“ he added.
Relations between Moscow and Kiev are at an all-time low since Russia's annexation of the Crimean peninsula from Ukraine in March and the subsequent outbreak of the pro-Russian rebellion in the east.
Pro-Western authorities in Kiev accuse Russia of orchestrating and arming the uprising after the overthrow of President Yanukovych, but the Kremlin denies that it is behind the revolt.
Ukraine crisis: A timeline of the conflict
Ukraine crisis: A timeline of the conflict
1/22 30 November 2013
Public support grows for the “Euromaidan” anti-government protesters in Kiev demonstrating against Yanukovych’s refusal to sign the EU Association Agreement as images of them injured by police crackdown spread.
2/22 20 February 2014
Kiev sees its worst day of violence for almost 70 years as at least 88 people are killed in 48 hours, with uniformed snipers shooting at protesters from rooftops.
3/22 22 February 2014
Yanukovych flees the country after protest leaders and politicians agree to form a new government and hold elections. The imprisoned former Prime Minister, Yulia Tymoshenko, is freed from prison and protesters take control of Presidential administration buildings, including Mr Yanukovych's residence.
Genya Savilov/AFP/Getty Imageses
4/22 27 February 2014
Pro-Russian militias seize government buildings in Crimea and the new Ukrainian government vows to prevent the country breaking up as the Crimean Parliament sets a referendum on secession from Ukraine in May.
Sean Gallup/Getty Images
5/22 16 March 2014
Crimea votes overwhelmingly to secede from Ukraine and join Russia in a ballot condemned by the US and Europe as illegal. Russian troops had moved into the peninsula weeks before after pro-Russian separatists occupied buildings.
6/22 6 April 2014
Pro-Russian rebels seize government buildings in the eastern cities of Donetsk, Luhansk and Kharkiv, calling for a referendum on independence and claiming independent republic. Ukraine authorities regain control of Kharkiv buildings on 8 April after launching an “anti-terror operation” but the rest remain out of their control.
7/22 7 June 2014
Petro Poroshenko is sworn in as Ukraine's president, calling on separatists to lay down their arms and end the fighting and later orders the creation of humanitarian corridors, since violated, to allow civilians to flee war zones.
8/22 27 June 2014
The EU signs an association agreement with Ukraine, along with Georgia and Moldova, eight months after protests over the abandonment of the deal sparked the crisis.
LOUISA GOULIAMAKI/AFP/Getty Images
9/22 17 July 2014
Malaysian Airlines flight MH17 is shot down over eastern Ukraine, killing all 298 people on board. Ukrainian intelligence officials claim it was hit by rebels using a Buk surface-to-air launcher in an apparent accident.
10/22 22 August 2014
A Russian aid convoy of more than 100 lorries enters eastern Ukraine and makes drop in rebel-controlled Luhansk without Government permission, sparking allegations of a “direct violation of international law”.
11/22 29 August 2014
Nato releases satellite images appearing to show Russian soldiers, artillery and armoured vehicles engaged in military operations in eastern Ukraine.
12/22 8 September 2014
Russia warns that it could block flights through its airspace if the EU goes ahead with new sanctions over the ongoing crisis and conflict
13/22 17 September 2014
Despite the cease-fire and a law passed by the Ukrainian parliament on Tuesday granting greater autonomy to rebel-held parts of the east, civilian casualties continued to rise, adding to the estimated 3,000 people killed
14/22 16 November 2014
The fragile ceasefire gives way to an increased wave of military activity as artillery fire continues to rock the eastern Ukraine's pro-Russian rebel bastion of Donetsk
15/22 26 December 2014
A new round of ceasefire talks, scheduled on neutral ground in the Belariusian capital Minsk, are called off
16/22 12 January 2015
Soldiers in Debaltseve were forced to prepare heavy defences around the city; despite a brief respite to the fighting in eastern Ukraine, hostilities in Donetsk resumed at a level not seen since September 2014
17/22 21 January 2015
13 people are killed during shelling of bus in the rebel-held city of Donetsk
18/22 24 January 2015
Ten people were killed after pro-Russian separatists bombarded the east Ukrainian port city of Mariupol
19/22 2 February 2015
There was a dangerous shift in tempo as rebels bolstered troop numbers against government forces
20/22 11 February 2015
European leaders meet in Minsk and agree on a ceasefire in eastern Ukraine beginning on February 14. From left to right: Belarus President Alexander Lukashenko, Russian President Vladimir Putin, German Chancellor Angela Merkel, France's President Francois Hollande and Ukrainian President Petro Poroshenko.
MAXIM MALINOVSKY | AFP | Getty Images
21/22 13 February 2015
Pro-Russian rebels in the city of Gorlivka, in the Donetsk region, fire missiles at Ukrainian forces in Debaltseve. Fighting continued in Debaltseve for a number of days after the Minsk ceasefire began.
ANDREY BORODULIN | AFP | Getty Images
22/22 18 February 2015
Ukrainian soldiers repair the bullet-shattered windshield of their truck as their withdraw from the strategic town of Debaltseve. Following intense shelling from pro-Russian rebels, Ukrainian forces began to leave the town in the early hours of February 18.
Brendan Hoffman | Getty Images
Nato claimed to have evidence of Russian involvement in the conflict, publishing satellite images of what it said was Russia soldiers and artillery in eastern Ukraine in August.
The alliance has strengthened its air presence in the Black Sea as well as its Baltic Air Policing mission throughout the Ukrainian conflict and has reported “near misses” between member states and Russian jets.
Nato has conducted more than 100 intercepts of Russian aircraft in 2014 - three times more than were conducted in the whole of 2013 – and increased tensions prompted Finland’s President to warn that Europe was being pushed to the brink of a "new kind of Cold War".
Additional reporting by agencies