The Verkhovna Rada - Ukraine's parliament - has approved opposition leader Arseniy Yatsenyuk as prime minister, Anadolu Agency reported.
Earlier in the day, Yatsenyuk challenged Yanukovych's claim that he remained the country's legitimate president. Yatsenyuk told reporters Yanukovych is a criminal, wanted on charges of murder and crimes against humanity, referring to the dozens of protesters killed during three-months of protests.
European diplomats are headed to Ukraine for meetings with the new government and acting President Oleksandr Turchynov.
Meanwhile, up to one thousand pro-Russian demonstrators in the Crimean capital of Simferopol pushed their way past a police barricade to hold a demonstration in front of the Crimean parliament.
Other pro-Russian demonstrators were seen arriving in the city from Sevastopol to join the protests. The groups demand a referendum to decide Crimea's future.
Crimean MPs have re-entered the parliament building after it was occupied on Thursday.
The political situation in Crimea has been tense since Ukraine was hit by large-scale protests that forced Yanukovych to flee Kiev after dozens were killed in street protests.
Yanukovych's policy to align the country with Russia was met with widespread opposition in November 2013 after he scrapped a major trade and association deal with the European Union.