After the 1990 season, Calderón was acquired by the Montreal Expos, in a multi-player deal that sent Tim Raines to the White Sox. The Expos raised Calderón's salary to over $2 million a season, and he earned a spot on the National League's roster for the 1991 MLB All-Star Game. He batted 1-for-2 in the All-Star Game, and had a stolen base. Calderón batted a career-high .300 during the 1991 season. Injuries during 1992 limited him to 48 games with Montreal that year. Overall in two seasons with the Expos, Calderón batted .291 with 22 home runs and 99 RBIs in 182 games.