The application of biodegradable and eco-friendly poly(lactic acid) (PLA) nanofibrous membranes (NFMs) toward respiratory healthcare has long been thwarted by the poor electroactivity and low surface activity of PLA. Herein, we unravel a microwave-assisted route to fabricate rod-like ZnO nanodielectrics, which were decorated with dopamine (ZnO@PDA) and anchored at the PLA nanofibers via an electrospinning–electrospray approach. The PLA/ZnO@PDA NFMs featured a substantially elevated specific surface area (up to 20.7 m2/g), increased dielectric constant (nearly 1.8) and a surface potential as high as 9.5 kV, resulting in superior air filtering performance (99.45% for PM0.3, 94.1 Pa, 32 L/min) compared with the pure PLA counterpart (90.04%, 169.0 Pa, 32 L/min). The notably increased electroactivity endowed the PLA/ZnO@PDA NFMs with significant improvements in triboelectric properties (output voltage of 11.5 V at 10 N, 0.5 Hz), laying down the cornerstone for self-powered monitoring of personal respiration. More importantly, a deep learning-assisted diagnostic system was developed based on respiration-driven signal patterns, enabling intelligent and real-time disease diagnosis with 100% accuracy for the protective membranes. The proposed hierarchical nanodecoration strategy opens up new possibilities for engendering eco-friendly nanofibers with an exceptional combination of efficient respiratory healthcare and intelligent diagnosis.