Fabrics consisting of cotton‐core/polypyrrole (PPy)‐sheath fibers (cotton/PPy fabrics) are synthesized by aqueous chemical oxidative seeded polymerization of pyrrole and are utilized as a solar evaporation device. Scanning electron microscopy studies and elemental microanalyses reveal the thickness of the PPy sheath increases from a few tens nm to ≈200 nm with an increase of pyrrole monomer concentration in the polymerization system. The temperature of cotton/PPy fabrics increases upon irradiation with artificial sunlight to ≈33–45 °C in the dry state, due to light‐to‐heat photothermal conversion by the PPy component. Thanks to the photothermal property of the fabrics, water impregnated within the cotton/PPy fabrics can evaporate efficiently under the irradiation of artificial sunlight. Light‐induced water evaporation experiment using an artificial seawater confirms that ionic concentrations drastically decreases, indicating successful desalination.