OBJECTIVE Ideal breathable and waterproof materials contain two key elements: hydrophobic matrix and small pore size. Current high-performing breathable waterproof membranes usually employ fluorinated materials to construct hydrophobic surface, which possess alarming potential environmental hazards. Fluorine-free waterproof agents through coating treatment to obtain hydrophobicity suffer from complicated fabrication process and poor durability. Hence, non-fluorinated chemicals incorporated into fibers via a facile one-step electrospinning may be an effective approach to attain durable hydrophobic membranes. METHODS Poly(methylhydrosiloxane)/polyurethane (PMHS/PU) solution with various PMHS concentration was formulated and electrospun to fibrous membranes, followed by a facile thermal treatment process. A systematic study including morphologies, porous structure, and surface wettability was performed. Breathable waterproof performance and tensile strength were also investigated. RESULTS Added PMHS imparted mighty hydrophobicity to the membranes with a water contact angle of 130.2°, and the subsequent heat treatment greatly improved waterproofness, meanwhile doubled the tensile strength. The resultant membranes exhibited robust hydrostatic pressure of 54.1 kPa, medium breathability of 9.5 kg m-2 d-1, and excellent stretching stress of 14.1 MPa, which can meet the requirements of general use. The presented strategy on membrane fabrication is feasible and scalable, which may be considered as an effective remedy for environmental protection.