Final answer:
Joe Montana threw the most touchdown passes to Jerry Rice, making them one of the greatest quarterback-receiver duos in NFL history and leading the 49ers to multiple Super Bowls.
Step-by-step explanation:
The quarterback who threw the most touchdown passes to Jerry Rice, the legendary wide receiver, was Joe Montana. During their time together on the San Francisco 49ers, Montana and Rice formed one of the most formidable quarterback-receiver duos in NFL history. As Rice's primary quarterback from 1985 to 1992, Montana's precise passing and Rice's exceptional route-running and catching abilities led to numerous touchdowns and contributed to the 49ers' success during that era, including multiple Super Bowl victories.