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Abstract For the need of direct contact with the skin, electronic skins (E‐skins) should not only fulfill electric functions, but also ensure comfort during wearing, including permeability, waterproofness, and easy removal. Herein, the study has developed a self‐adhesive, detach‐on‐demand, breathable, and waterproof E‐skin (PDSC) for motion sensing and wearable comfort by electrospinning styrene‐isoprene block copolymer rubber with carbon black nanosheets as the sensing layer and liner copolymers of N, N‐dimethylacrylamide, n‐octadecyl acrylate and lauryl methacrylate as the adhesive layer. The high elasticity and microfiber network structure endow the PDSC with good sensitivity and high linearity for strain sensing. The hydrophobic and crystallizable adhesive layer ensures robust, waterproof, and detaching‐on‐demand skin adhesion. Meanwhile, the fiber structure enables the PDSC good air and water permeability. The integration of electric and wearable functions endows the PDSC with great potential for motion sensing during human activities as both the sensing and wearable performances.