"I announce my resignation in connection with the dissolution of the parliamentary coalition and the blocking of government initiatives," a furious Yatsenyuk told parliament.
Yatsenyuk said the "government and the prime minister must resign" after the withdrawal of several parties triggered the break up of the European Choice parliamentary majority in a move that paved the way for long-awaited early legislative elections.
Parliament speaker Oleksandr Turchynov called on deputies to put forward immediately a candidate for a temporary premier "until parliamentary elections are held."
The formal dissolution of the majority coalition in Ukraine's Verkhovna Rada gives President Petro Poroshenko the right over the next month to announce a fresh parliamentary poll.
Poroshenko had pledged though that the possibility of upcoming elections would not paralyse the work of parliament at a time when Kiev is struggling to end a bloody separatist insurrection tearing apart the east of the country.