Solar-driven interfacial evaporation technology has shown significant potential in the field of water treatment. Heat loss is still inevitable during the SIE process, since the temperature at the evaporation interface surpasses both the ambient temperature and the temperature of the water below. In this study, we presented a study on an aerogel composed of reduced graphene oxide (rGO), multi-walled carbon nanotubes (MWCNTs) and polypyrrole (PPy). The self-aggregation effect of rGO was mitigated through π-π interactions with MWCNTs and PPy, resulting in the formation of a three-dimensional porous structure. This provided the aerogel with a large specific surface area for pollutant adsorption and ample pore volume for photo-induced degradation and photothermal water purification. Using infrared thermography, thermocouples and numerical simulation, it was demonstrated that introducing a cold evaporation surface resulted in thermal flow reversal. This process allowed the evaporator to extract energy from bulk water, thereby enhancing solar evaporation. Due to this gain, under one sun illumination, the aerogel reached an evaporation rate as high as 3.31 kg·m−2·h−1 and achieved an evaporation efficiency of 135.6 %. Simultaneously, the aerogel exhibited a photocatalytic efficiency of over 90 % for various organic pollutants (methylene blue trihydrate, trypan blue and tetracycline hydrochloride). Moreover, it also demonstrated excellent purification ability for combined wastewater, including high-salinity water, seawater and lubricant/water emulsions. Therefore, high-performance interfacial evaporators hold great promise for achieving sustainable wastewater purification and serve as a valuable reference for the development of new solar energy conversion systems.