Zhongchao Tan

Electrospun fibrous structures can be developed superhydrophobic while remaining breathable. However, current electrospinning‐based methods for developing superhydrophobicity require complex fabrication processes and multiple raw materials, lacking a facile approach to superhydrophobicity using electrospun fibers. Inspired by a cultural relic known as Plain Gauze Gown, a fibrous structure consisting two layers of porous fibers aligned in warp and weft directions by simple electrospinning is developed. Through investigation of wetting behavior, an unique Cassie–Baxter‐“restoring” (CaRe) wetting contributing to a stable Cassie–Baxter state is unveiled in the developed structure. The CaRe wetting ensures that droplet stays on the upper‐layer fibers even at a sparse inter‐fiber distance, enabling strategically reaching superhydrophobicity by lowering structure solidity. Remarkably, the developed structure with water contact angle between 159° and 162° and roll‐off angle from 10° to 3° has a water vapor transmission rate of 20.8 kg m −2 d −1 , which is the highest value among all superhydrophobic electrospun structures reported, and it is also waterproof and semi‐transparent. These features make the structure suitable for a wide range of applications, including developing waterproof, breathable, and superhydrophobic membrane with simple preparation and low cost, and as a surface layer for wearable electronics that facilitates sweat evaporation and prevents water intrusion.