Oleksandr Turchynov takes charge following the dismissal of President Viktor Yanukovych on Saturday. Mr Turchynov told MPs they had until Tuesday to form a new unity government.
Parliament also voted to seize Mr Yanukovych's luxury estate near Kiev, which protesters entered on Saturday.
The whereabouts of Mr Yanukovych, who described parliament's decision to vote him out as a coup, remain unclear.
Thousands of opposition supporters remain in Independence Square, where the atmosphere is described as calm.
Late on Saturday, former Prime Minister Yulia Tymoshenko, freed from detention in the eastern city of Kharkiv after a vote in parliament, urged opposition supporters in Independence Square to continue protesting.
Her release was one of the conditions of the EU-Ukraine trade pact that President Yanukovych rejected last year - triggering the protests that led to the current crisis.
The health ministry says 88 people, mostly protesters, are now known to have been killed since 18 February.
Mr Turchynov, a close associate of Ms Tymoshenko, described forming a unity government as a "priority task".
"We don't have much time," one of the opposition leaders, former world champion boxer Vitaly Klitschko, said as parliament began its debate.
Speaking to the BBC, he also suggested a bid for the presidency in elections scheduled for 25 May.
"I want to make Ukraine a modern European country," he said. "If I can do that through the president's position, I will do my best."
In other decisions on Saturday:
Foreign Minister Leonid Kozhara and Education Minister Dmytro Tabachnyk were dismissed
Arrest warrants were issued for former Incomes Minister Oleksandr Klimenko and former
Prosecutor-General Viktor Pshonka
Parliament lowered the official status of the Russian language by cancelling a law brought in by Mr Yanukovych
Mr Yanukovych refused to officially stand down. He is last thought to have been in Kharkiv after travelling there late on Friday night.
Media reports have quoted Ukrainian officials as saying he was stopped by border police while attempting to fly to Russia aboard a private plane.
MPs from Mr Yanukovych's Party of Regions now appear to be disowning him.
"Ukraine was betrayed and people were set against each other. Full responsibility for this rests with Yanukovych and his entourage," its MPs said in a statement carried by Interfax-Ukraine.
Source: BBC News
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