AbstractThe photoreforming reaction, which can produce hydrogen simultaneously with the decomposition of organic waste, is a promising method for resolving longstanding global issues such as the depletion of energy resources and climate change. However, ZnS photocatalysts, one of the most optimal catalysts for such reactions, has an inadequate visible‐light response; thus, the extensibility of the reaction is limited. In this study, CdS photocatalysts are prepared from metal–organic framework (MOF) precursors, that is, Cd‐MOFs. The prepared CdS exhibits high hydrogen production activity in the photoreforming of lignocellulosic biomass under quasi‐sunlight conditions. This activity is approximately 13.4 times that of the CdS prepared via the conventional hydrothermal method. Further, CdS can utilize light energy in the visible region of sunlight, providing a high quantum yield and demonstrating the potential for the extensibility of the reaction. The results of this study will facilitate the fabrication of novel materials for sustainable and efficient hydrogen production.