The frame structure combined with water-and heattransfer capabilities fully satisfies the requirements of photothermal conversion materials in seawater evaporation applications. Meanwhile, it must integrate the characteristics of a high photothermal conversion rate, thermal management, and water transportation. Herein, lamellar porous films were successfully designed and synthesized by a simple ultrasonic-assisted vacuum filtration method. In this process, polystyrene sulfonate@carbon nanotubes/reduced graphene oxide (PSS@CNT/rGO) lamellar films were constructed by the one-dimensional synthesis of PSS@CNT self-assembled at the molecular scale and the two-dimensional matrix material rGO. It is worth noting that the lamellar film exhibits a high specific surface area (285.5 m 2 •g −1 ), which is reflected in its abundant nanopores. Among them, the porous network system composed of nanochannels can provide efficient water supply and steam-transfer ability and strengthen the heat insulation performance of thermal localization, which is beneficial to photothermal evaporation. The obtained PSS@CNT/rGO lamellar films achieved a condensed water yield of 1.825 kg•m −2 •h −1 under 1 sun illumination (1 kW•m −2 ), and their solar-vapor conversion efficiency was 97.1%. Simultaneously, the interaction between the water flow and the carbon material interface was also used to generate additional electric energy output. The maximum open-circuit voltage of 0.46 V was generated at both termini of the PSS@ CNT/rGO lamellar film, which successfully realized the multieffect utilization of energy. These results show that the multistage assembly strategy is a facile and effective means for the development of an efficient evaporation photothermal film, which offers significant value in the field of photothermal seawater evaporation and power generation.