Skin-like functional membranes with liquid resistance and moisture permeability are in growing demand in various applications. However, the membranes have been facing a long-term dilemma in balancing waterproofness and breathability, as well as resisting internal liquid sweat transport, resulting in poor thermal–wet comfort. Herein, a novel electromeshing technique, based on manipulating the ejection and phase separation of charged liquids, is developed to create triboelectric nanostructured nano-mesh consisting of hydrophobic ferroelectric nanofiber/meshes and hydrophilic nanofiber/meshes. By combining the true nanoscale diameter (≈22 nm), small pore size, and high porosity, high waterproofness (129 kPa) and breathability (3736 g m−2 per day) for the membranes are achieved. Moreover, the membranes can break large water clusters into small water molecules to promote sweat absorption and release by coupling hydrophilic wicking and triboelectric field polarization, exhibiting a satisfactory water evaporation rate (0.64 g h−1) and thermal–wet comfort (0.7 °C cooler than the cutting-edge poly(tetrafluoroethylene) protective membranes). This work may shed new light on the design and development of advanced protective textiles.