Police in the town of Costesti deployed more than 3,000 men and fired tear-gas in a vain attempt to force the miners - who numbered about 7,000 - to retreat, but after a two-hour battle the strikers emerged victorious.
Troops had piled massive concrete slabs across the road to deter an onslaught, but around midday, hundreds of miners in cars and trucks attacked the line with rocks and missiles. The attack was reinforced as thousands more miners arrived at the scene.
Antenna 1 private television said a policeman was shot to death during the clashes but there was no official confirmation. The television station also reported that about 50 police officers had been taken hostage. National television, citing the Health Ministry, reported at total of 138 people injured, 130 of whom were said to be police.
The miners later stopped for the night at Ramnicu Valcea, 100 miles north- west of Bucharest, where they staged noisy anti-government protests.
In an effort to keep the miners from Bucharest, the government has cut all rail links between Ramnicu Valcea and the capital, and set up barriers manned by anti-riot police on roads connecting the two cities. About 5,000 police have been stationed at the main road-block, about 25 miles outside the capital.
The Interior Minister, Gavril Dejeu, who has been widely criticised for failing to stop the miners' advance, was fired yesterday. He was replaced by Constantin Dudu Ionescu, a former deputy defence minister.
"Miners are attacking in an organised way, like an army," said a government spokesman. "They have taken prisoners among the policemen."
The authorities are desperate to prevent miners descending on Bucharest, fearing violent protests. In previous visits to the capital in 1990 and 1991, miners went on the rampage for days, leaving nine people dead, dozens injured and forcing the government to resign.
The Prime Minister, Radu Vasile, earlier named a government team to negotiate with the miners, but miners rejected the offer, insisting the premier be present at any talks.
Coming out of an emergency government meeting, President Emil Constantinescu said the conflict was "damaging the authority of the state".
He later convened the Supreme Defence Council - a crisis body consisting of himself, the Prime Minister, the ministers of defence and interior, top military and police officers and the heads of Romania's intelligence services. They debated whether to curtail civil rights by declaring a state of emergency.
The miners, who have been on strike for 16 days, are seeking a 35 per cent wage rise and the equivalent of pounds 6,000 severance pay - demands the government says it cannot afford. Miners make pounds 120 a month - about double the average wage.
Yesterday's clash was the second outbreak of violence this week. Twenty- four miners and police were injured on Monday, the day the miners began their march. (AP)