This paper investigates three typical structural damages of photovoltaic pavements and proposes a slab-column reinforced hollow slab photovoltaic pavement structure (SCPP). The SCPP comprises a base layer reinforced by a “slab-column” system, a photovoltaic layer, and a transparent surface layer. A reasonable three-dimensional finite element model was developed for mechanical analysis. The safety and dimensional rationality of the SCPP were validated by comparing its mechanical responses with those of a conventional hollow slab structure under identical loading conditions. The results demonstrate that the SCPP effectively reduces vertical displacement and equivalent stress under applied loads, with minimum safety factors for both the base structure and the transparent surface layer exceeding 5. The proposed dimensions for the SCPP are as follows: Transparent surface layer: 46 cm × 46 cm × 2 cm, Photovoltaic layer: 135 mm × 135 mm × 2 mm, Base layer: 50 cm × 50 cm × 6 cm, with groove width and depth both at 20 mm, a cross-sectional radius of the quarter-column reinforcement of 30 mm, and a slab width of 30 mm. The proposed photovoltaic pavement structure satisfies road loading requirements and offers a valuable reference for the advancement of photovoltaic pavement technology.