Lawmakers in Berlin's glass-domed Reichstag voted 364-315 with nine abstentions for Merkel who was then to be formally appointed by President Frank-Walter Steinmeier before taking the oath of office at 1100 GMT.
German Chancellor Angela Merkel renewed a promise on Wednesday that the migrant influx of 2015 won't be repeated as she embarks on her fourth term. "That's no way to operate".
President Muhammadu Buhari on Tuesday extended his "sincere congratulations" to President Vladimir Putin of Russian Federation on his victory in the country's recent presidential election. She sent him "warm" congratulations this week after the Russian leader was elected to a new six-year term as president.
Mrs Merkel set out her mission to overcome polarisation in Germany in a speech in the Bundestag to mark the start of the new government.More news: #Enough: It's time to talk about gun control
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Merkel, 63, outlined her new government's agenda and highlighted a polarized country facing a range of threats from trade to a stable currency. But she added: "Of course, it's also the case that this was an exceptional humanitarian situation".
"Although our nation is in good shape and the economy is doing better than at any time since reunification, many people are anxious about the future", Merkel said.
The election, which came after four years in which Merkel's conservative Union bloc and the center-left Social Democrats had an overwhelming majority, weakened the governing parties and saw the anti-migration Alternative for Germany, or AfD, enter parliament for the first time.