Nanofiber-based facial masks have attracted the attention of modern cosmetic applications due to their controlled drug release, biocompatibility, and better efficiency. In this work, Azadirachta indica extract (AI) incorporated electrospun polyvinyl alcohol (PVA) nanofiber membrane was prepared to obtain a sustainable and hydrophilic facial mask. The electrospun AI incorporated PVA nanofiber membranes were characterized by scanning electron microscope, Ultraviolet-visible spectroscopy (UV-Vis) drug release, water absorption analysis, 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging, and antibacterial activity (qualitative and quantitative) at different PVA and AI concentrations. The optimized nanofiber of 376 ± 75 nm diameter was obtained at 8 wt/wt% PVA concentration and 100% AI extract. The AI nanoparticles of size range 50~250 nm in the extract were examined through a zeta sizer. The water absorption rate of ~660% and 17.24° water contact angle shows good hydrophilic nature and water absorbency of the nanofiber membrane. The UV-Vis also analyzed fast drug release of >70% in 5 min. The prepared membrane also exhibits 99.9% antibacterial activity against Staphylococcus aureus and has 79% antioxidant activity. Moreover, the membrane also had good mechanical properties (tensile strength 1.67 N, elongation 48%) and breathability (air permeability 15.24 mm/s). AI-incorporated nanofiber membrane can effectively be used for facial mask application.