Napoleon played baseball, football, basketball and track at Morrisville High School in Morrisville, PA. Shortly after graduation, his father passed away. While playing at Rider University, he caught the eye of the Mets, and signed as an amateur free agent with them prior to the 1964 season.
He batted .351 with 36 home runs and 134 runs batted in his first year of professional baseball to carry the Auburn Mets to a 79-48 record and first place in the New York–Penn League. In order to protect him from being selected in the minor league draft, the Mets added him to their 40 man roster.
Napoleon made his major league debut on April 14, 1965 in the eleventh inning of an extra innings affair with the Houston Astros. He singled off Hal Woodeshick in his first major league at bat. Ten days later, Napoleon hit a pinch hit bases loaded triple off the San Francisco Giants' Bob Shaw for his first three major league RBIs.

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