Olivo was signed by the Milwaukee Braves in 1955 (by then already 27 years old), but didn’t make his major-league debut until June 1961 at age 33. He pitched a total of 2 innings across 3 games, then headed back to the minors until 1964.
Chi-Chi pitched 38 games for the Braves during the 2nd half of 1964, but it wasn’t enough to secure a long-term job with the club. After 2 games in April 1965, he was sent back down until returning in September for another 6 games.
Olivio’s final season with the Braves was 1966. He stayed with the Braves for most of the season, picking up 7 saves in 47 games. He also spent 6 weeks in the minors in August and September.
After the 1966 season he was traded to the Yankees with outfield prospect Bill Robinson for 3rd baseman Clete Boyer. He pitched in triple-A all season before retiring.
Olivio made a brief comeback in the Mexican League in 1971 and 1972.
He passed away in 1977 at age 48.
His brother Diomedes Olivo pitched for the Pirates and Cardinals in 1962 and 1963.