Jim Montgomery was still playing Tier Two hockey in Pembroke at the age of 19, where he scored 53 goals and 154 points in 50 games. In not being drafted, Montgomery decided the best career move would be to pursue an education. He played in the NCAA with the University of Maine for four seasons beginning in 1989-90. He was a consistent scorer throughout his collegiate career, always surpassing 20 goals and in his senior year had 32 goals to go along with his 63 assists for 95. Only Paul Kariya's 100 points were higher. The school also won the NCAA championship that year and Montgomery was named the NCAA Tournament Championship MVP and was picked as an NCAA East Second Team All-American
Montgomery signed with the St. Louis Blues as a free agent in the summer of 1993 and played 67 games with the team in his rookie year. The next offseason he was dealt to his hometown Canadiens for Guy Carbonneau but played in just five games with the Habs.
The Philadelphia Flyers claimed Montgomery off waivers in February, 1995 but again his playing time was limited to just five games. He decided to try his hand at playing in Germany for a year but returned to Philadelphia where he played with the Phantoms of the AHL for two years. He played with the San Jose Sharks in 2000-01. The Dallas Stars signed him to a free-agent deal in the summer of 2001 but he has not played with them. In 2001-02 Montgomery played in the AHL with the Utah Grizzlies.