Tim Barrow, who will take charge as the UK's Permanent Representative (UKRep) to the EU next week, is a senior diplomat known as a "tough negotiator".
He replaces Ivan Rogers, who resigned unexpectedly on Tuesday expressing concerns over a "muddled" Brexit strategy.
"We are delighted that Tim Barrow is taking up this role. A seasoned and tough negotiator, with extensive experience of securing UK objectives in Brussels, he will bring his trademark energy and creativity to this job - working alongside other senior officials and Ministers to make a success of Brexit," a Downing Street spokesperson said.
He previously served as the UK Ambassador to Moscow and before that he worked as UK Representative to the Political and Security Committee of the EU from 2008-11.
His earlier EU experience includes spells as an Assistant Director in the Europe Directorate and UKRep First Secretary.
"I am honoured to be appointed as the UK's Permanent Representative to the EU at this crucial time. I look forward to joining the strong leadership team at the Department for Exiting the EU and working with them and the talented staff at UKRep to ensure we get the right outcome for the United Kingdom as we leave the EU," he said.
UK foreign secretary Boris Johnson said, "Tim Barrow has been invaluable since I joined the Foreign Office in July and I want to personally thank him for his relentless energy, wise counsel and steadfast commitment".
"He is just the man to get the best deal for the UK and will lead UKRep with the same skill and leadership he has shown through his career. I wish him all the best," he said.
The new appointment follows Rogers' stormy exit whose resignation note to colleagues in Brussels seemed to indicate that UK ministers were not fully in control of Brexit parleys.
Opposition Labour has demanded a statement from the government when Parliament returns from its Christmas and New Year break on Monday.
The prime minister is expected to spell out some of her Brexit plans by the end of this month and trigger Article 50 of the Lisbon Treaty to kick off formal negotiations for Britain's departure from the 28-nation economic bloc by March-end.
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