Tusk, who speaks only halting English and no French, is the first eastern European to hold such a senior post in the EU and is known as a tough critic of the Kremlin, especially over the Ukraine crisis.
"The suspense is up, the new EU leadership team is complete," said current EU President Herman Van Rompuy moments after the announcement was made yesterday.
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"I come to Brussels from a country that deeply believes in the significance of Europe," the centre-right Tusk told a news conference with Van Rompuy and Mogherini.
Tusk will take office on December 1 while Mogherini, if confirmed by the European Parliament, will start her new job on November 1.
Strongly backed by German Chancellor Angela Merkel, the 57-year-old Tusk is a pro-European free marketeer with roots in Poland's Solidarity anti-Soviet trade union who has been prime minister since 2007.
Merkel said Tusk "faced big challenges" and lauded him as "a qualified, committed and passionate European, 25 years after the fall of the Berlin Wall, 25 years after the end of the Cold War."
He will also head up summits of the countries that use the euro, despite years of questioning the wisdom of eurozone bailouts as prime minister and Poland not being a member of the single currency.
Tusk denied his poor command of foreign languages would handicap him as EU president, a job that requires a deft touch to find compromise amid conflicting positions and prepare European leaders for often delicate summits.
"Don't worry, I will 'Polish' my English and be 100% ready on December 1," Tusk said in English, punning on the word for his nationality and showing a command of the language one journalist openly questioned at the press conference.
Mogherini, Italy's 41-year-old foreign minister, has long been a favourite to replace Catherine Ashton as head of the EU's foreign service, hailed by her supporters as a new, younger face for Europe.
"I hope I can join the new energy of the new European generation that is there not only among the EU citizens but also in the EU political leadership," Mogherini said.
With leaders unnerved by Russia's latest actions in Ukraine, the nomination of Tusk to replace Belgium's Van Rompuy could send a message of resolve to Moscow as EU leaders also mull fresh sanctions against Moscow.
Mogherini's candidacy initially faced fierce resistance, with Eastern European countries -- and reportedly British officials -- criticising her as both inexperienced and too soft on Russia.
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