Waterproof and breathable membranes (WBMs) have drawn broad attention due to their widespread applications in various scientific and industry fields. However, creating WBMs with environment-friendliness and high performance is still a critical and challenging task. Herein, an environmentally friendly fluorine-free WBM with high performance was prepared through electrospinning and one-step dip-coating technology. The fluorine-free waterborne hydroxyl acrylic resin (HAR) emulsion containing long hydrocarbon chains endowed the electrospun polyacrylonitrile/blocked isocyanate prepolymer (PAN/BIP) fibrous membranes with superior hydrophobicity; meanwhile, crosslinking agent BIP ensured strong chemical binding between hydrocarbon segments and fiber substrate. The as-prepared PAN/BIP@HAR fibrous membranes achieve ideal properties with waterproofness of 112.5 kPa and moisture permeability of 12.7 kg m-2 d-1, which are comparable to the existing high-performance fluorinated WBMs. Besides, the PAN/BIP@HAR membranes also display impressive tensile strength and durability. Significantly, the proposed technology was also applicable to other hydrophilic fiber substrates, such as cellulose acetate and polyamide 6. The successful synthesis of environmentally friendly, durably waterproof, and highly breathable PAN/BIP@HAR membranes not only opens a new avenue to materials design, but also provides promising candidates with tremendous potential in various areas.