Salmon graduated from Abel Bravo High School in Colon, Panama where he lettered in baseball, basketball, and track. He later attended Abel Bravo College, where he also played baseball. It was as a college student that Salmon played for the Panamanian baseball team during the 1959 Pan-American Games in Venezuela. Shortly after playing in that tournament, Chico was signed by the Pacific Coast League's Denver club of the Milwaukee Braves organization.
Salmon was selected by the Seattle Pilots in the expansion draft following the 1968 season, but was acquired by the Orioles for Gene Brabender and Gordon Lund on March 31, 1969.
Salmon was not particularly well-known for his fielding. While he was still with the team, the Orioles had a mock award named the Chico Salmon No Touch Award "to recognize fielding prowess that had all the deftness of a rhinoceros knitting," according to Jim Palmer. He was, however, widely known for his belief in ghosts which caused him to always sleep with the lights on.

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