There is limited research on the fracture toughness of carbon-fiber-reinforced polymer (CFRP) materials under accelerated UV aging conditions. In this study, the primary focus was on investigating the influence of varying durations of ultraviolet (UV) irradiation at different temperatures on the Mode I, Mode II, and mixed-mode fracture toughness of CFRP laminates. The results indicate that with increasing UV aging duration, the material’s Mode I fracture toughness increases, while Mode II fracture toughness significantly decreases. The mixed-mode fracture toughness exhibits an initial increase followed by a subsequent decrease. Furthermore, as the aging temperature increases, the change in the fracture toughness of the material is more obvious and the rate of change is faster. In addition, the crack expansion of the composite layer of crack-containing Type IV hydrogen storage cylinders was analyzed based on the extended finite element method in conjunction with the performance data after UV aging. The results reveal that cracks in the aged composite material winding layers become more sensitive, with lower initiation loads and longer crack propagation lengths under the same load. UV aging diminishes the overall load-bearing capacity and crack resistance of the hydrogen storage cylinder, posing increased safety risks during its operational service.