Solar-driven cogeneration systems integrating photovoltaic (PV) technology with waste-heat-driven interfacial evaporation offer a sustainable route to the simultaneous production of electricity and water vapor. However, salt accumulation in conventional contact-based interfacial evaporators remains a major obstacle to long-term operation. Contactless evaporation (CLE) physically separates the solar absorber from the saline feed, thereby preventing direct brine contact and salt deposition on the absorber surface. Nevertheless, CLE has not yet been explored for PV-enabled electricity–water-vapor cogeneration. Here, we propose a photovoltaic-enabled contactless evaporation (PV–CLE) system in which PV cells positioned above the water surface generate electricity, while their residual heat drives contactless evaporation across an air gap via thermal radiation. The use of semi-transparent PV (STPV) cells further allows transmitted near-infrared solar radiation to directly heat the water while mitigating PV overheating, thereby enabling more effective full-spectrum solar utilization. A coupled three-dimensional multiphysics model incorporating a spectral-splitting framework is developed to elucidate the interacting optical, electrical, thermal, and mass-transport processes within the proposed system. Three representative PV technologies, namely crystalline silicon (c-Si), cadmium telluride (CdTe), and perovskite solar cells (PSCs), are systematically evaluated over a range of ambient temperatures, relative humidities, wind speeds, and air-gap thicknesses and benchmarked against an absorber-only CLE system. The results reveal distinct performance trade-offs: c-Si achieves the highest solar-to-electricity efficiency (19.2%), CdTe delivers the highest solar-to-vapor efficiency (45.8%), and the PSC-based system attains the highest overall equivalent efficiency of 78.8% at an air-gap thickness of 5 mm, representing a 155% increase relative to the absorber-only CLE reference system. Under baseline conditions, the PSC-based system operates at approximately 42.2 °C, which is 14.8 °C lower than the operating temperature of the c-Si system. These findings establish PV–CLE as a promising technology for efficient electricity and water-vapor cogeneration, advancing sustainable solutions at the water–energy nexus.