CEO Michael Corbat tapped Jamie Forese and Manuel Medina-Mora for the roles.
Corbat took over as CEO of the New York company in October after Vikram Pandit unexpectedly stepped down from the post.
Forese will be responsible for all of Citi's institutional businesses, and Medina-Mora will continue to oversee global consumer banking and Citi's franchise in Mexico.
Forese had served as CEO of securities and banking for the institutional clients group.
Corbat also named Jim Cowles as CEO of the company's Europe, Middle East and Africa division a position previously held by Corbat.
Citigroup Inc.'s stock shed 25 cents to $42.18 in morning trading.