The Russian-made Sputnik V Covid-19 shot is first being offered to doctors and other medical workers, teachers and social workers.
Sergei Sobyanin, the mayor of Moscow, said 5,000 doctors, teachers and social workers signed up for the vaccine in five hours.
The age for those receiving shots is capped at 60, and people with certain underlying health conditions, pregnant women and those who have had a respiratory illness for the past two weeks are barred from vaccination.
Russia has developed two Covid-19 vaccines, Sputnik V which is backed by the Russian Direct Investment Fund and another developed by Siberia’s Vector Institute.
The vaccines have received regulatory approval in Russia, but final clinical trials to test the safety and efficacy of both are yet to be completed.
Scientists have raised concerns about the speed at which Russia has worked.
Interim trials showed Sputnik V is 92 per cent effective at protecting people from Covid-19.
The vaccine is administered in two injections, with the second dose is expected to be given 21 days after the first.
Moscow, the epicentre of Russia’s coronavirus outbreak, closed down all public places including parks and cafes, except for deliveries, in late March and police patrolled the streets looking for those violating the rules.
The restrictions were eased from mid-June, but certain measures, such as remote learning for some secondary school children and a 30 per cent limit on the number of workers allowed in offices, were reintroduced in October.
Russia reported a record high 28,782 new coronavirus infections on Saturday, pushing the national total to 2,431,731 since the pandemic began, the fourth-highest in the world.
Of the new cases, 7,993 were in Moscow. This was up from 6,868 the day before and well above the daily tallies of around 700 seen in early September.
Authorities confirmed 508 coronavirus-related deaths in the past 24 hours, pushing the national death toll to 42,684.