Solar steam generation (SSG) is a promising technology for the production of freshwater that can help alleviate global water scarcity. Nanostructured metals, known for their localized surface plasmon resonance effect, have generated significant interest, but low-cost metal films with excellent water evaporation properties are challenging. In this work, we present a one-step dealloying route for fabricating self-supporting black nanoporous zinc (NP-Zn) films with a bicontinuous ligament/channel structure, using Al-Zn solid solution alloys as the precursors. The influence of alloy composition on the formation and macro/microstructure of NP-Zn was investigated, and an optimal Al98Zn2 was selected. Additionally, in situ and ex situ characterizations were conducted to unveil the dealloying mechanism of Al98Zn2 and phase/microstructure evolution of NP-Zn during dealloying, including the phase transition of Al(Zn) → Zn, significant volume shrinkage (89.8%), and the development of high porosity (81.3%). The nanoscale ligament/channel structure and high porosity endow the NP-Zn films with good broadband absorption and superior hydrophilicity and, more importantly, give them excellent SSG performance. The NP-Zn2 film displays high evaporation efficiency, superior stability, and good seawater desalination performance. The efficient SSG performance, material abundance, and low cost suggest that NP-Zn films have promising applications in metal-based photothermal materials for SSG.