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The blast on Saturday afternoon was thought to have been fuelled by an accumulation of methane, according to United Press International.
Mediafax reported that the five workers were servicing an electric transformer at the time of the explosion, which was estimated to be 400 metres underground.
The first sign of the explosion reportedly came from smoke exiting the ventilation system. Mine rescuers went underground and recovered the bodies five hours later.
The mine was undergoing weekend maintenance when the explosion occurred.
The old government-owned mine is reportedly due to close in 2018 and has a workforce of around 800.
The mine is in the Jiu Valley, also home to the Petrila mine where 12 people died from two blasts in 2008.
