Serbian President Boris Tadic has dissolved parliament, calling snap elections for 11 May.
Mr Kostunica (left) said his cabinet could not agree on a policy
The move follows last week's collapse of the governing coalition led by Prime Minister Vojislav Kostunica.
Ministers failed to agree on whether to suspend ties with the European Union, in protest at recognition of Kosovan independence by some EU members.
EU officials have said they hope Serbia's pro-EU parties will win the May elections.
The fresh ballot is seen as a way out of Serbia's deepening political crisis, says the BBC's Helen Fawkes in Belgrade.
"The elections are a democratic way for citizens to say how Serbia should develop in years to come," President Tadic said in a statement.
Mr Kostunica, who leads the Democratic Party of Serbia (DSS), says recognition of Kosovo by major EU states is illegal.
"All parties want Serbia to join the EU, but the question is how - with or without Kosovo," he said last week.
President Tadic says Belgrade will only be able to defend its right to Kosovo if it joins the EU.
He says the main difference between himself and his prime minister is not on Kosovo but Serbia's "European and economic outlook".
Kosovo's declaration of independence on 17 February came nearly a decade after Nato forces expelled Serbian forces from the majority ethnic Albanian territory.
The US and most EU states have recognised Pristina's unilateral move.
Serbia and its ally Russia say they will never accept it.