This article presents a novel plasma-assisted nonsolvent-induced phase separation (PANIPS) method to fabricate superhydrophobic, self-cleaning, and piezoelectric poly(vinylidene difluoride) (PVDF) membranes without additional chemical modifications or post-treatments. The PANIPS membranes exhibit water contact angles ranging from 151.2° to 166.4° and sliding angles between 6.7° and 29.7°, with a high piezoelectric coefficient (d33) of 10.5 pC N⁻¹ and can generate a high output voltage of 10 Vpp. These membranes effectively recover pure water from various waste solutions containing Rose Bengal dye, humic acid, or sodium dodecyl sulfate via direct contact membrane distillation (DCMD). The study highlights the potential of PANIPS membranes in clean water production, motion sensor, and piezoelectric nanogenerator applications. The PANIPS method involves plasma treatment of as-cast membranes to create multilevel roughness, increase surface porosity, and suppress macrovoid formation. Plasma treatment induces a unique crystalline phase transition from non-electroactive α-phase to electroactive γ-phase, enhancing the piezoelectric performance of PVDF membranes. The morphological and physicochemical properties of PVDF membranes can be adjusted by controlling plasma treatment parameters such as scan cycle, scan speed, and working distance. The PANIPS membranes exhibit remarkable piezoelectric performance with a maximum output voltage of >10 Vpp and excellent resistance to various aqueous solutions. They also demonstrate higher flux, greater salt rejection, and superior long-term stability compared to NIPS membranes when treating feed solutions containing 10 wt% NaCl and Rose Bengal via DCMD. The study also investigates the effects of plasma treatment on membrane superhydrophobicity and crystalline phases. Plasma treatment generates charged water ion clusters that interact with the membrane surface, creating hierarchical micro/nano structures and inducing solid-liquid demixing, which renders the membrane superhydrophobic. The plasma treatment also induces a phase transition from α-phase to γ-phase, enhancing the electroactive properties of PVDF membranes. The PANIPS method is a facile, green, and efficient approach to fabricate superhydrophobic, self-cleaning, and piezoelectric membranes, offering a promising alternative to traditional methods. The study suggests that further research is needed to explore the effects of different reaction gases and precursors in the dope solutions to tailor the physicochemical properties of membranes.This article presents a novel plasma-assisted nonsolvent-induced phase separation (PANIPS) method to fabricate superhydrophobic, self-cleaning, and piezoelectric poly(vinylidene difluoride) (PVDF) membranes without additional chemical modifications or post-treatments. The PANIPS membranes exhibit water contact angles ranging from 151.2° to 166.4° and sliding angles between 6.7° and 29.7°, with a high piezoelectric coefficient (d33) of 10.5 pC N⁻¹ and can generate a high output voltage of 10 Vpp. These membranes effectively recover pure water from various waste solutions containing Rose Bengal dye, humic acid, or sodium dodecyl sulfate via direct contact membrane distillation (DCMD). The study highlights the potential of PANIPS membranes in clean water production, motion sensor, and piezoelectric nanogenerator applications. The PANIPS method involves plasma treatment of as-cast membranes to create multilevel roughness, increase surface porosity, and suppress macrovoid formation. Plasma treatment induces a unique crystalline phase transition from non-electroactive α-phase to electroactive γ-phase, enhancing the piezoelectric performance of PVDF membranes. The morphological and physicochemical properties of PVDF membranes can be adjusted by controlling plasma treatment parameters such as scan cycle, scan speed, and working distance. The PANIPS membranes exhibit remarkable piezoelectric performance with a maximum output voltage of >10 Vpp and excellent resistance to various aqueous solutions. They also demonstrate higher flux, greater salt rejection, and superior long-term stability compared to NIPS membranes when treating feed solutions containing 10 wt% NaCl and Rose Bengal via DCMD. The study also investigates the effects of plasma treatment on membrane superhydrophobicity and crystalline phases. Plasma treatment generates charged water ion clusters that interact with the membrane surface, creating hierarchical micro/nano structures and inducing solid-liquid demixing, which renders the membrane superhydrophobic. The plasma treatment also induces a phase transition from α-phase to γ-phase, enhancing the electroactive properties of PVDF membranes. The PANIPS method is a facile, green, and efficient approach to fabricate superhydrophobic, self-cleaning, and piezoelectric membranes, offering a promising alternative to traditional methods. The study suggests that further research is needed to explore the effects of different reaction gases and precursors in the dope solutions to tailor the physicochemical properties of membranes.