Eleven parties are competing for places in the lower house, the Duma - though it is not clear how many will win the 7% needed to qualify for seats.
Opposition parties have accused the government of stifling their campaigns and of intimidation.
Independent monitors say their attempts to observe the poll have been hampered.
The Organization for Security and Co-operation in Europe (OSCE) has abandoned its plans to send a big team of election observers to Russia after accusing the Russian government of imposing unacceptable restrictions and of deliberately delaying the issuing of visas. Russia has denied the claims.
Only a much smaller group of MPs from the OSCE's parliamentary assembly will be in attendance.
That means just 400 foreign monitors will cover 95,000 polling stations.
The British ambassador in Moscow, Tony Brenton, told the BBC he said it appeared there had been what he called imbalances and misuses of the administration in this election.
The largest party in the Duma going into the elections is United Russia, and it will be hoping to maintain its dominance against the challenge from the Communist Party, the Liberal Democratic Party, the Yabloko party and others.
Russian President Vladimir Putin is at the top of the United Russia party list - opening the possibility that he could keep a grip on power from parliament even after stepping down as president next year.
Within Russia the media is banned from referring to parties, politicians, policies or opinion polls for the duration of the election.
Far east start
Voting began at 0800 on Sunday (2000 GMT, Saturday) in Russia's far easterly region of Kamchatka, about 6,000km (3,700 miles) east of Moscow.
Voting is not set to end until 22 hours later, when polls are due to close in the enclave of Kaliningrad, on the Baltic Sea, 11 time zones to the west.
Sailors in the far east port of Vladivostok waited at a polling station to cast their votes on Sunday morning.
"I'll vote for United Russia," Vladimir Babikov, 19, told the AFP news agency.
"They've done a good job, everything is getting better."
In Petropavlovsk-Kamchatsky, Alexei Gutkin, a 42-year-old engineer, voted for the centre-right Union of Right Forces.
"United Russia is like a return to the Communist Party," he said. "I remember that time well."
'Farce'
The run-up to the vote has been marred by increasing allegations that the poll could be rigged.
Opposition rallies have been broken up, parties have complained that their headquarters have been raided, and that state media has been a mouthpiece for the government.
The former chess grandmaster and Kremlin critic Garry Kasparov has dismissed the elections as a "farce". His political grouping is one of several to be barred from contesting the poll.
More than 100 million voters are eligible to cast ballots at 95,000 polling stations across the country, with about 450,000 police officers reportedly on duty to ensure order.
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