Photothermal desalination driven by solar energy has emerged as a promising strategy for freshwater and clean energy production. One of the great challenges in interfacial evaporation is simultaneous achievement of superior freshwater production, salt harvesting, and electricity generation in an evaporator. Herein, an all‐inclusive photothermal solar steam generator using high‐performance photothermic converting film is reported, featuring in interconnected fibrous network, broadband absorption, heat insulation, and unidirectional water transfer. The superior characteristics can readily form a constant salinity gradient in system during vaporization, not only realizing the spatial isolation of evaporation and salt crystallization zones to harvesting freshwater and salt separately, but more importantly achieving continuous electricity generation from salinity gradient power without trade‐offs. Such stable solar steam generator integrated with efficient photothermal converting material and rational structural design highlights the practical consideration toward solar distillation by deep desalination, which can not only sustainably achieve the freshwater and salt production, but collaboratively generate the electricity for emergency needs.