Solar‐driven interfacial vaporization by localizing solar‐thermal energy conversion to the air–water interface has attracted tremendous attention due to its high conversion efficiency for water purification, desalination, energy generation, etc. However, ineffective integration of hybrid solar thermal devices and poor material compliance undermine extensive solar energy exploitation and practical outdoor use. Herein, a 3D organic bucky sponge that has a combination of desired chemical and physical properties, i.e., broadband light absorbing, heat insulative, and shape‐conforming abilities that render efficient photothermic vaporization and energy generation with improved operational durability is reported. The highly compressible and readily reconfigurable solar absorber sponge not only places less constraints on footprint and shape defined fabrication process but more importantly remarkably improves the solar‐to‐vapor conversion efficiency. Notably, synergetic coupling of solar‐steam and solar‐electricity technologies is realized without trade‐offs, highlighting the practical consideration toward more impactful solar heat exploitation. Such solar distillation and low‐grade heat‐to‐electricity generation functions can provide potential opportunities for fresh water and electricity supply in off‐grid or remote areas. Organic solar absorber sponge with a broadband light absorption and inbuilt cellular structure performs efficient interfacial photothermic vaporization. The solar‐to‐vapor conversion efficiency can be remarkably enhanced by compressing or isolating from bulk water. In addition, the complementary thermoelectric power generation induced by solar heat stored in the sponge can be achieved during the solar vaporization.