The woman found a 9mm handgun left behind by a security guard at her office in Moscow and decided take a selfie while posing with the firearm.
Holding the gun close to her head, the young woman accidentally pulled the gun's trigger and shot herself through the temple.
A spokesperson for the Moscow's Sklifosovsky hospital said the woman was in a "serious condition" after she was brought to the Moscow clinic on Thursday.
The owner of the gun is now facing up to six months behind bars for negligent weapon possession, RIA Novosti news agency reported.
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Police are investigating how the woman got hold of the gun as the security guard, who was on holidays when the tragic incident occurred, had secured the weapon in the office.
The trend for posting selfie photographs online has prompted risky behaviour worldwide.
On Saturday, a Singaporean man died in Bali after falling off a cliff while taking a selfie. Mohammed Aslam Shahul, 21, lost his balance and fell into the sea off a cliff while on vacation with his friends.