Abstract Solar‐powered interfacial evaporation presents a sustainable approach for water purification, but the presence of volatile organic compounds (VOCs like phenol) poses significant challenges to its efficacy. Herein, an innovative catalytic evaporator constructed from Balsa wood functionalized with coordination polymers (cobalt‐1,5‐diamino‐4,8‐dihydroxyanthraquinone, Co‐DDA) is introduced. This multifunctional Co‐DDA exhibits both conductive and catalytic characteristics, facilitating photothermal evaporation and photothermal catalysis within an integrated platform. The resultant evaporator achieves an impressive evaporation rate of 3.23 kg m −2 h −1 and an energy efficiency of 89.0% under one‐sun irradiation. Notably, the local heat‐induced molecular deformation of the Co‐DDA polymer facilitates the reduction in the energy barrier of persulfate adsorption, as supported by experimental and simulation data. This effect promotes persulfate activation to generate more reactive oxygen species, resulting in a remarkable 97.0% degradation for 50 mg L −1 phenol. Furthermore, the Co‐DDA‐Balsa evaporator demonstrates exceptional long‐term salt resistance and high antimicrobial activity, ensuring efficient, stable, and eco‐friendly solar‐driven water purification. This work sheds light on the development of multifunctional and sustainable catalytic evaporators for highly efficient VOC removal during interfacial evaporation.