Abstract: Conventional fossil fuel dependence and energy-intensive seawater desalination technologies intensify resource shortage and environmental degradation within the strained global water–energy nexus. Solar-driven interfacial evaporation (SDIE) technology has broken through the conventional evaporation efficiency bottleneck through the “thermal localization” strategy. The water–electricity cogeneration technology, which integrates multiple energy capture mechanisms, offers an innovative solution to the water–energy paradox. This paper provides a comprehensive review of recent advances in SDIE for water–electricity cogeneration. First, strategies for enhancing water production efficiency are analyzed in four aspects, thermal layer optimization, advanced thermal management, evaporation stability optimization, and reduced evaporation enthalpy. Then, the synergistic integration principles between the evaporation system and multiple categories of energy conversion modules, including thermoelectric generation, hydroelectric effects, salinity gradient electricity, triboelectric and piezoelectric are comprehensively explored. Optimization pathways for energy density and conversion efficiency are critically compared and analyzed. Finally, the review summarizes persistent technical challenges and proposes future research directions.