The development of multifunctional membranes integrating asymmetric wettability, breathable waterproofing, antibacterial activity, and energy-harvesting capabilities is critical for smart textiles and medical protective equipment, yet balancing robustness, environmental adaptability, and energy conversion efficiency remains challenging. Here, we engineer a bioinspired Janus nanofibrous membrane with a spider-web-like hierarchical architecture via synchronous electrospinning-electrospraying of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and polyamide 6 (PA6). This design achieves dual-scale wettability (hydrophobic/hydrophilic asymmetry), 83.6% porosity, and mechanical durability (99% structural integrity after 2000 bends). It enables intelligent environmental regulation (7.4 ℃ thermal gradient under 1 kW/m² solar irradiation), while the electric-field-enhanced design accelerates water transport by 20% vs. passive diffusion. Its triboelectric performance surpasses existing breathable membranes (177.5 V open-circuit voltage, 0.63 W/m2 power density, stable output over 10,000 cycles), enabling encrypted Morse-code communication for programmable human-machine interaction. The hierarchical structure exhibits exceptional antibacterial efficacy: 99.92% against Escherichia coli (E. coli), 100% against methicillin-resistant Staphylococcus aureus (MRSA), and 95% against Staphylococcus aureus (S. aureus). Via a scalable, low-cost process compatible with roll-to-roll manufacturing, this approach holds promise for industrial integration in next-generation wearable healthcare and protection systems.