Aidan James, 27, is charged with one count of preparation of acts of terrorism and two of attendance at a place used for terrorist training.
The father-of-one, from Formby, Merseyside, was arrested at Liverpool Airport on 14 February. He will appear at Westminster Magistrates' Court later.
It follows after a former British Army soldier was charged with a terror offence last week.
James Matthews appeared at Westminster Magistrates’ Court on 14 February to be formally accused of attending a “place used for terrorist training”.
He denies travelling to Syria to fight against Isis and is due to appear at the Old Bailey on 1 March.
The Government has repeatedly warned that anyone travelling to join a foreign conflict may be prosecuted – but the cases involving the two men are the first of their kind.
Anti-Isis volunteers have been arrested and questioned, with former volunteer Joshua Walker acquitted of unrelated terror charges over possessing a copy of the Anarchists Cookbook.
The dozens of British volunteers believed to be fighting with Kurdish People’s Protection Units (YPG) against Isis are vastly outnumbered by around 850 extremists who travelled from the UK to join the terrorist group.
The YPG is considered a terrorist organisation by the Turkish government, but its fighters have received backing from the West in the war in Syria.