The move will see Hector Sants switching sides from heading the Financial Services Authority to overseeing all compliance activities in all regions in which Barclays does business, the bank said.
"I left the FSA with the intention of finding a role which would allow me to put into practice the experience I have gained in both the public and private sector," Sants, 56, said in a statement.
The bank was hit by scandal earlier this year when British and U.S. regulators fined it 290 million pounds ($467 million) for manipulating a key interbank lending rate known as LIBOR.
Barclays said that Sants, who stepped down as the FSA's chief executive in June, will serve as Barclay's first point of contact for governments and regulators around the world.
He will take up the post on Jan. 21 and report directly to Barclays' group chief executive, Antony Jenkins, who replaced Bob Diamond at the top after the LIBOR scandal pushed several members of the bank's board to step down.
Jenkins has been keen to see his bank become what he called the "go-to bank" for setting compliance standards.
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