He will share power with Viktor Yushchenko, the president who ousted him in 2004.
The president said he had guarantees from Yanukovich that he would not try to reverse the revolution's pro-Western principles.
Yanukovich, who held the prime minister's job before the revolution, gained 271 votes from the 450 deputies in parliament.
His supporters applauded his victory and presented him with a bouquet of red flowers.
"I am itching to get down to work," he said before the vote. "I've been ready [to serve as prime minister] for a long time," Yanukovich told reporters.
The coalition deal ended a parliamentary deadlock that had been holding up key decisions for months and left Ukraine without a fully-fledged government and Constitutional Court.
Many supporters of the Orange Revolution say Yanukovich will use his new power to check Ukraine's drive to join Nato and the European Union. They also say business interests close to him will have undue influence over economic policy.
But markets expect pragmatic economic policies under Yanukovich and his team. They gained a reputation as competent managers during their previous stint in government.
Ukraine's "Orange" camp fell
apart from infighting
Yanukovich and his allies - who now include the president's Our Ukraine party - also dominate the country's new cabinet, but under the constitution Yushchenko has control of key ministries such as foreign affairs and defence.
The jobs of first deputy prime minister and the interior minister will go to a Yushchenko ally, said a senior Our Ukraine official.
Ukrainian media pointed to Petro Poroshenko, a wealthy businessman, as the most likely candidate for deputy prime minister.
Mykola Azarov, a technocrat who oversaw economic and financial policy during Yanukovich's last premiership from 2002-2004, will be finance minister, said media reports.
Arseniy Yatsenyuk, the 31-year-old economy minister, was expected to keep his job.
Relationship with Russia
Yanukovich's comeback owes much to fighting within the "Orange" camp. Their first government fell apart and they ran as competing parties in a March election, allowing Yanukovich to form a majority in parliament.
Yanukovich favours closer ties with Moscow, but mass protests in 2004 overturned his election as president and swept Yushchenko to power.
In an interview with Russia's Izvestia, Yanukovich said fixing the faltering economy required a better relationship with Russia.
"If we accept Russia as a partner, than we will be able to solve our biggest problems, including over gas," he said.
Russia's state gas giant Gazprom briefly cut off supplies to Ukraine in January in a dispute over contracts. It is now warning of a second hike in prices, which are a crucial factor in Ukraine's economy.