"Sixty-five people were killed and the fate of 35 others is unknown," ministry spokesman Igor Krol told AFP, adding that 28 miners had been hospitalised.
A total of 456 people were in the Zasyadko mine in the eastern Donetsk region when the explosion occurred at 5.41 a.m. yesterday, a spokesman for the emergency situations ministry said.
A massive rescue operation continued through the day with 65 rescue teams and more than 20 medical units at the scene, the emergency situations ministry said in a statement.
Grim-faced rescuers wearing hard hats and carrying oxygen tanks prepared to descend into the mine, where officials said a fire was still raging.
"I don't know what happened. I heard a bang and the air started to get hotter," miner Vitaly Svetkovsky, 30, said at a local hospital, his eyes circled in coal dust.
The hospital's chief doctor Yevgeny Gadchuk said most of the miners hospitalised were suffering from methane inhalation. "They're in a state of shock," he said.
Hundreds of desperate family members gathered by the entrance to the mine looking for news of their loved ones.
"I detest them, these mines," said a middle-aged woman, in tears as she tried to track down a relative.
Officials periodically came out of an administrative building with names of those who were confirmed as dead.
"Dear friends, we have some new surnames: Ershov, Pavlenko..." an official said. The names were met with cries from relatives.