Extensive research efforts have been recently devoted to the development of self-driven electrocatalytic water-splitting systems to generate clean hydrogen chemical fuels. Currently, self-driven electrocatalytic water-splitting devices are powered by solar cells, which operate intermittently, or by aqueous batteries, which deliver stored electric power, leading to high operating costs and environmental pollution. Thus, a fully solar-powered uninterrupted overall water-splitting system is greatly desirable. Here, the solar cells, stable output voltage of 1.75 V Ni-Zn batteries, and high efficiency zinc-nickel-cobalt phosphide electrocatalysts are successfully assembled together to create a 24 h overall water-splitting system. Specifically, the silicon-based solar cells enable the charging of aqueous Ni-Zn batteries for energy storage as well as providing sufficient energy for electrocatalysis throughout the day; in addition, the highcapacity Ni-Zn batteries offer a steady output voltage for overall water-splitting at night. Such an uninterrupted solar-to-hydrogen system opens up exciting opportunities for the development and applications of renewable energy.