Abstract: As a potential fire scenario for bridge structures, the safety impact of an FRP anti-collision floating pontoon fire on bridge structures cannot be ignored. Taking the FRP anti-collision floating pontoon fire that occurred in a continuous rigid-frame bridge as the engineering background, the damage condition of the actual bridge fire scene was first investigated. In addition, FDS 5.3 software was used to simulate the FRP anti-collision floating pontoon fire scenario. Furthermore, the thermal–structural coupling method was used to investigate the thermodynamic response of double-armed thin-walled piers under fire. The results show that the FRP anti-collision floating pontoon fire causes localized concrete carbonization and spalling on the surface of the P2 pier, and the FRP anti-collision floating pontoons are largely destroyed. The fire has the greatest impact on the P2-1 pier, with the highest temperature of 667 °C on the windward side and the highest temperature of 326 °C on the leeward side. The temperature impact range is 6 m above the bearing platform, and the maximum damage depth of pier body concrete is 84.58 mm. The deformation and stress of the P2 pier under fire do not show significant changes and do not exceed the allowable limits for structural deformation and material stress. Therefore, the impact of this fire accident on the structural safety of the continuous rigid-frame bridge is minor. This study's results provide reliable guidance for the fire safety assessment and post-fire structural repair of the continuous rigid-frame bridge.