The corrosion behaviors of two bridge steels (Q345q and Q500q) under simulated ultraviolet irradiation and a wet–dry alternating (UVWD) environment were studied. Weight loss measurement, stereomicroscope observation, SEM, XRD, and electrochemical impedance spectroscopy (EIS) were performed to investigate the influence of the coupled environment. The results revealed that the corrosion rates of Q345q and Q500q were significantly accelerated by the synergistic effect of UV light exposure and alternating wet–dry conditions. Numerous voids and cracks could be observed throughout the thickened rust layers, enabling the corrosive substances to easily penetrate through the rust layer. Q500q exhibited better corrosion resistance than Q345q due to the addition of Mo, Cr, and Ni as corrosion-resistant elements, which tended to transform the rust layer into α-FeOOH rather than γ-FeOOH during later stages of corrosion.