Parliament voted to oust conservative Prime Minister Janez Jansa, after smaller parties left his coalition.
He was accused by the anti-corruption watchdog in January of tax irregularities and has been struggling to implement austerity measures to combat the country's financial crisis.
MPs asked opposition leader Alenka Bratusek to form a new government.
She will become the first woman to lead Slovenia since its independence from Yugoslavia in 1991.
Mr Jansa was elected a year ago, but his government has struggled to contain the country's economic problems.
Slovenia joined the European Union in 2004 and the eurozone in 2007, but its banking sector was hit hard by the financial crisis and the eurozone crisis that followed.
It is currently in a deep recession, with unemployment at more than 12% and GDP expected to shrink by a further 2% this year.
There is speculation that Slovenia will be forced to request an international bailout, as it needs to repay 2bn euros (Â£1.7bn; $2.6bn) of debt in the coming months.
Mr Jansa has faced corruption allegations, but also growing public anger and protests over austerity measures.
Ms Bratusek, who has previously worked in the finance ministry, has voiced her opposition to austerity, saying her priority will be "growth and jobs".
She also plans to avoid requesting a Greece-style bailout. "I say it clear, there will be no Greek scenario in Slovenia," she told parliament.

The 34-year-old dominated opponent Aleksandr Nedovyesov for a 7-6 (7-2) 6-2 6-3 victory in the decisive singles rubber in Darwin.
Earlier Sam Groth levelled the tie against Mikhail Kukushkin.
Australia travel to Great Britain, who defeated France, for the last-four tie in September.
Neither Hewitt nor Groth had initially been selected to play singles but captain Wally Masur dropped youngsters Thanasi Kokkinakis and Nick Kyrgios after Kazakhstan had opened up a 2-0 lead.
They teamed up to reduce the deficit in the doubles before victories in their respective singles matches saw them come back to win from 2-0 down for the first time since 1939.
Hewitt, Wimbledon winner in 2002, embraced his team-mates after the victory, saying: "This is up there.  I love the back-against-the-wall situations. That's what we had after day one.
"We had to rally together and find a way to get the win.  I've always said some of my greatest wins are in Davis Cup and some of my toughest losses are in Davis Cup so I'm going to enjoy this one. This is what dreams are made of."

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After a scoreless first period, James Desmarais fired a shot across Mike Clemente into the net for the Giants.
Taylor Dickin levelled and Cody Cartier scored the decisive goal just 43 seconds into the third period.
The Giants remain six points behind leaders Cardiff Devils in the standings, with one game in hand.
Storm kept Jackson Whistle busy in the first period and the Giants netminder again excelled in the second period.
Belfast player-coach Derrick Walser rattled the outside of the post in the second period and the visitors soaked up Giants pressure in the final minutes of the contest.
The Giants' next match is at home to Braehead Clan on Friday (19:00 GMT), the team they defeated 5-1 on Boxing Day.
After that, Coventry Blaze visit the SSE Arena on 2 January (16:00).
The government of Slovenia, beset by economic turmoil and allegations of corruption, has fallen.
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Former Wimbledon champion Lleyton Hewitt guided Australia into the Davis Cup semi-finals as the hosts came from 2-0 down to beat Kazakhstan 3-2.
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The Belfast Giants' unbeaten run of 10 games came to an end on Wednesday night with a 2-1 Elite League defeat by Manchester Storm at the SSE Arena.