The demand for environmentally friendly personal protective equipment (PPE) is high due to the coronavirus pandemic. However, conventional electrostatic-based surgical masks and healthcare apparel are single-use, non-biodegradable and often end up as mismanaged waste. Therefore, development of sustainable and biodegradable non-woven textiles is essential. The present work has demonstrated a novel sustainable approach for the fabrication of medical textiles for surgical mask from a substitute of food waste derived polymers polylactic acid (PLA) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) via electrospinning process. A polymer concentration of 12.5 % comprising an equal proportion of PLA and PHBV in formic acid resulted in stable electrospinning and defect-free nanofibers with a mean diameter of 323 ± 76 nm. A duallayer nanofiber membrane was able to achieve filtration efficiencies of over 99.5% and over 96.2% for 1–5 μm and 0.3 μm particulates, respectively, while maintaining high breathability with differential pressure less than 5 mm  H₂O/cm². The fabricated nanofibrous membrane attributed the necessary characterizations as per the ASTM-F2100 standard. Importantly, nanofiber membrane with an equal proportion of PLA and PHBV has the best overall biodegradation performance. Degradation was significant within 4 weeks in both composting and marine conditions, achieving over 99% and 90% degradation respectively.