• A novel electrospinning method creates ordered honeycomb and spinous dual-coupled microstructures in nanofibrous membranes, enhancing mechanical, breathability, and sensing performance.
• The electronic skin exhibits a 276% increase in pressure sensitivity and a 137% increase in detection range compared to conventional random porous membranes.
• The device achieves real-time, interference-free dual-modal sensing of pressure and temperature with a maximum temperature coefficient of resistance of −0.918 °C−1.
• The skin-conformal and breathable design, using ionic liquid functionalized nanofibrous membranes, enables comfortable and reliable wearable applications.