However, the rivalry most frequently cited for having the most games played is Army vs. Navy. While the exact number fluctuates depending on the source and how precisely "game" is defined (including scrimmages etc), it's widely accepted they've played well over 100 times, and are consistently near or at the top of any such list.
Other rivalries with a very high number of games include those between teams in close geographic proximity playing regularly for decades or centuries, but pinning down the precise "most" is a significant research undertaking.