Water and electricity shortages constitute a global energy crisis that cannot be ignored. The sun is an unlimited source of energy, and oceans provide abundant water and renewable energy resources. In this study, poly-(vinylidene fluoride) (PVDF)/graphene solar evaporator membranes are fabricated for simultaneous freshwater production and power generation. Graphene addition transformed the PVDF crystal from the α-phase to the piezoelectric self-assembly β-phase. The resulting membrane is used to convert the mechanical energy of waves to electrical energy. The membrane has an output voltage of 2.6 V (±1.3 V) and an energy density of 2.11 Wm −2 for 1 Hz simulated waves, which are higher than values reported in the literature. The stacked graphene and polymer formed a wood-lumens-like mesoporous structure with a photothermal effect. Under one sun illumination, the water production rate is 1.2 kg m −2 h −1 , and the solar-thermal energy conversion efficiency is 84%. Finally, a prototype is built to prove a single evaporator's feasibility that can simultaneously obtain freshwater and generate electricity. Thus, this membrane serves as an ocean wave power generation device that can provide all-weather energy generation, convert stored electrical energy into thermal energy at night and on cloudy days, and continuously provide safe drinking water.