Efficient solar absorption and photoinduced charge separation are extremely important for solar-energy conversion on semiconductor photocatalysts. To advance the photocatalytic performance, we developed a general templated-assisted reverse cation exchange strategy to successfully synthesize hollow-structured CdS semiconductors with the textile structural surface. The crystal phase, particle morphology, optical/electrical properties, and photocatalytic performance of the as-syntheszied sample are investiagted by XRD, SEM, TEM, XPS, DSR, PL, ESR photoelectrochemical measurements, and Photocatalytic H 2 evolution test. The final CdS sample exhibits an enhanced photocatalytic hydrogen evolution rate of up to 965 μmol·g−1 h−1, 2.8 times higher than the reported CdS nanorods. Based on the experimental and characterization results, the improved photocatalytic activity of the cadmium sulfide semiconductor can be ascribed to the special hollow cubic structure with a thin shell, which can enhance the light-harvesting ability and provide abundant photocatalytic active sites for facilitating the separation of photogenerated electron/hole pairs. This synthetic strategy may pave a new path for the rational design of efficient sulfur-based semiconductor photocatalysts for solar driven H 2 production. Hollow-structured CdS cubes have been successfully synthesized via reverse cation exchange strategy for enhanced photocatalytic hydrogen production. [Display omitted] • CdS nanocubes were synthesized via templated-assisted cation exchange strategy. • CdS exhibits enhanced photocatalytic H 2 evolution rate of up to 965 μmol·g−1 h−1. • The photocatalytic performance is attributed to hollow structure of CdS nanocubes. • This strategy may pave a new way for rational design of efficient photocatalysts. [ABSTRACT FROM AUTHOR]