LONDON — Tom King, one of Citigroup Inc.'s top executives in Europe, is leaving the U.S. banking giant after 20 years there and will likely take a senior position at Barclays PLC's investment bank, according to people familiar with the matter.

Mr. King, 48, is Citigroup's London-based head of corporate and investment banking and capital markets for Europe, the Middle East and Africa. In the new role he is expected to take at Barclays, Mr. King would help the U.K. bank build its investment-banking franchise in Europe, the people said, cautioning that it isn't yet certain he will join Barclays.

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