The waterproof and moisture permeable fabric with thermal regulation not only has the protective function forhuman body, but also meets the comfort of human clothing, which is a challenging and innovative research. Herein, we reportan environmentally friendly, simple, and high-efficiency strategy to fabricate waterproof and breathable nanofibermembranes with outstanding thermal regulation ability by introducing stearic acid (SA) into the hydrophobic siliceouspolyurethane (SIPU) solution by a facile one-step electrospinning. Owing to the addition of SA, the waterproofness of SIPU/SA nanofiber membranes is greatly improved, meanwhile, the addition of SA acted as a phase change material to imparttemperature regulation performance in appropriate temperature range to the SIPU/SA nanofiber membranes. By adjusting theaddition amount of the SA, eco-friendly and multifunctional SIPU/SA nanofiber membranes are systemically optimized withgood waterproofness (79 kPa), moisture breathability (8.0 kg m-2 d-1), and outstanding temperature regulation performance(latent heat up to 40 J/g), satisfied tensile strength (6.2 MPa) and excellent breaking elongation of 182 %. The obtained SIPU/SA nanofiber membranes can be suitable for the design of multifunctional wearable textiles for various applications,especially in outdoor protective clothing, medical clothing, intelligent clothing and military products.