He was initially signed by the Pittsburgh Pirates as an amateur free agent in 1980, but was released prior to the start of the 1982 season. In 1984 he was signed by the Tigers, spending five seasons in their minor league organization before making his major league debut in 1989. Since Ramón was in the American League while Tony was playing for the St. Louis Cardinals of the National League, and since interleague play didn't begin until 1997, the two brothers never played against each other in the major leagues.

His career was much shorter and less successful than those of his two relatives. In eight career regular season games, had a lifetime earned run average of 6.00, allowing twelve earned runs in eighteen innings, as well as a WHIP of 1.89. Although he didn't earn a decision in any of his eight appearances, he didn't pitch a game in which his team earned the win. He made his major league debut on April 27, 1989 against the California Angels at Anaheim Stadium in Anaheim, California. Peña surrendered three runs on seven hits in 2 ²⁄₃ innings in a relief appearance in a 10-3 Tigers loss. Oddly, despite his rather high 6.00 earned run average, he did not surrender a home run to any of the 88 batters he faced in the major leagues.

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