AbstractInterfacial evaporation has emerged as a promising approach to produce freshwater. However, an urgent concern is that, due to the illegal discharge of industrial wastewater, most water bodies are polluted by trace volatile organic compounds (VOCs), which are easily volatilized and enriched in the collected water during the interfacial evaporation process. Herein, a bilayer photothermal evaporator was reasonably designed for contaminated water purification. The bottom hydrophilic rGO‐sodium alginate (SA) sheets purposefully disintegrate water transport channels, thus quickly removing VOCs through physical adsorption. The rGO‐SA‐TiO₂ upper layer sufficiently absorbs incident light and therefore persistently generates reactive oxidizing species to degrade upward VOCs. Notably, the oriented microchannels inside the evaporator allow sustained light reflections to improve the utilization of solar energy. The evaporation rate can reach 1.63 kg m⁻² h⁻¹ with a considerably high VOC removal efficiency of up to 96 %. Such an integrated bilayer evaporator provides an effective strategy to obtain clean water via solar distillation.