A novel proof‐of‐concept strategy to enhance the evaporation rate (ER) and solar conversion efficiency of the solar‐driven interfacial evaporation (SDIE) technique is presented. This strategy is able to employ photovoltaic (PV) electricity for powering photothermal convertor, thus the photoinduced electrons from the nanocomposite of carbon dots (CDs) and CuS can be fully converted into heat for rapidly vaporizing seawater. The presented system enables a steam generation rate of above 6.66 kg m −2 h −1 with a solar‐to‐vapor efficiency of up to 183% in 3.5% salt brine under one sun. Such high performance is ascribed to the instantaneous release of more heat energy within the confined photothermal layer, resulting in the vaporization of more water adsorbed in this layer. Moreover, the experimental results reveal that the solar evaporation performances of the presented system are determined by the applied voltages and interfacial charge transfer efficiency of the sunlight harvesting agent under constant solar illumination.