The first riders reacted enthusiastically to the red bicycles stationed at some 30 stations along the city centre's boulevards, but many said they were too nervous about the traffic to brave the capital's large, busy streets and would continue to use the metro for their daily commute.
"It's a promising idea, they have done this in many European cities," said one young man who introduced himself as Andrei after trying out the system.
"As soon as there are also bike paths, people will also ride them on large roads," he told AFP. "Also respect between drivers and bicyclists is not developed enough yet."
The scheme is similar to ones already in place in cities like Paris, London and more recently New York.
To start with, there are just 150 bikes available for hire, though authorities say they plan to rapidly expand the service.
In a system similar to those in other countries with bike-sharing schemes, users have to register online and deposit money into an account before they can access the urban bicycle stations, which are for now concentrated around Moscow's central boulevard ring.
The bikes, which are free for the first half hour and cost 30 rubles ($1) per hour after that, can be returned to any station after use.
Despite road safety concerns, the Russian capital has seen a surge in cycling in recent years, with many shopping malls now offering bike racks and the city's parks and riverfronts often crowded with cyclists.
Commuting by bicycle in car-dominated Moscow however remains a daunting challenge for many as there are no designated bike lanes on major streets and parked cars often crowd the sidewalks.
Bicycles are forbidden on the Moscow metro, while buses and trams are not equipped with special racks for bikes, making long trips across the expansive city difficult.
Pensioner Tamara Makarova was among the onlookers examining the new bicycles with interest, but she said she would never try one on a main road. "I'm afraid," she said. "There are too many cars."
Moscow city hall has announced that it will develop a total of 131 kilometres (81 miles) of cycle paths by the end of this year, a small figure compared with other large cities around the world.
"Cycling will develop and in two years maybe it will find a compromise with cars, and drivers will understand that cyclists are also a part of the city," said rider Vitaly as he sat on a bench next to his newly-rented bike.
The city has promised to widen the network to 120 locations and expand outside the centre by the end of July. The system will close at the end of October ahead of winter.