The accident happened at around 10.20am at a paper mill of Vinh Phat JSC in the Phu Bai industrial zone.
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A worker was said to inhale methane in an underground paper pulp settling tank and scream for help. Five other workers jumped down and they were all suffocated with the toxic gas, without wearing safety goggles or breathing masks.
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Rescue workers were called in to pull the six victims out of the tank and bring them to the centrally-run Hue hospital.
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Colonel Le Quoc Hung, Deputy Director of the Thua Thien Hue provincial Police Department, said two workers were dead at the scene and four others currently remain in critical condition.
Relevant agencies are conducting further investigations into the accident.