In this study, energy, exergy, exergoeconomic and exergoenvironmental (4E) assessment of new integration of solar still with photovoltaic module (PV) is performed. This new integration is based on installing the PV module over the back side of the solar still while its output electrical power is converted directly to thermal heat to heat the saline water in the basin. The main advantage of such integration is that it does not occupy an extra area more than the land area occupied by the solar still. Furthermore, this integration makes the PV as a reflector that transferring its reflected solar energy to the solar still basin. Four systems of solar stills are examined and compared; conventional solar still (CSS), solar still with photovoltaic module (CSS + PV), solar still with PV and black steel wool fibers in the basin (CSS + PV + BSWF) and solar still with PV used as a reflector only (CSS + PV reflector). The experiments for the proposed systems are conducted in summer season at climate conditions of Alexandria, Egypt. Results indicated that the inclusion of CSS + PV, CSS + PV + SF, and CSS + PV as a reflector in solar still enhances the modified still energy efficiency by 10%, 31.48%, 43.16%, respectively compared to CSS. Whereas, the corresponding value of exergy efficiency is also enhanced by 30.72%, 49.14%, and 680.7%, respectively. The application of PV with solar still was found ineffective in terms of energy payback time compared to CSS. Also, the exergoeconomic and exergoenvironmental evaluations of solar still with PV indicate promising results compared to those of conventional still. Overall, using PV as a reflector with solar still system is found to be the most effective system from the exergoeconomic and exergoenvironmental perspectives considering the current PV prices and production technologies.