Fire broke out in Hospital No 14 in Ramenskiy shortly after 02:00 (22:00 GMT Thursday), when most of the victims are believed to have been asleep.
Investigators say an alarm went off but the duty nurse only managed to evacuate two patients because of heavy smoke.
Reports suggest a patient who ignored a smoking ban may have started the fire.
It quickly consumed the one-storey, brick-and-wood building.
Firefighters dispatched to the scene took more than an hour to arrive instead of the standard 20 minutes because a river crossing had been closed due to flooding, Russian media report.
Several fires at state institutions across Russia in recent years resulted in heavy loss of life.
In 2009, 23 people died in a blaze at an old people's home in Komi while in 2007, 63 died at a home in Krasnodar. In 2006, a fire at a Moscow drug rehabilitation clinic killed 45 women.
According to a list of victims being circulated online, 36 were patients and two were members of staff.
Believed to be local people, they ranged in age from 76 to 20.
A statement by Russia's Investigative Committee says that, according to preliminary information, the source of the fire was a sofa used in a common room.
A surviving patient told investigators that a drug addict had been admitted with withdrawal symptoms on Thursday, and had been smoking constantly despite warnings from staff.
The Investigative Committee added that it was examining other theories such as a short circuit or arson.
A fire safety inspection was carried out at the hospital last year and action taken to improve safety measures, the hospital's chief doctor, who was not named, told Russian media.
The doctor described the patients who died as a "very tough group of people, psychiatric patients with chronic illnesses and frequent attacks" who had suffered from alcohol and drug addiction.
Patients were under sedation and most of them did not wake up, emergencies official Yuri Deshevykh told Russia's RIA Novosti news agency.
Bars on windows may also have been a factor in the high death toll.
A police source quoted by Interfax news agency said that following the blaze, a hole 1.5m (yds) deep was found beneath the charred remains of the building.
One of the patients may have been digging an escape tunnel, the source added.
Source: BBC News
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