The exploration for a suitable cocatalyst to substitute noble metals is crucial to establishing an efficient photocatalytic system. In this study, a facile solution‐based approach is employed to integrate sheet‐like NiSe2 nanostructure as a cocatalyst onto ultrafine ZnCdS nanoparticles, with the objective of enhancing photocatalytic H2 production. Notably, the optimized 3% NiSe2/ZnCdS photocatalyst exhibits a remarkable enhancement in photocatalytic H2 evolution rate, achieving 7779 μmol g−1 h−1, representing an 8.3‐fold increase compared to ZnCdS. Furthermore, the NiSe2/ZnCdS demonstrate exceptional stability during cycling tests. The impressive photocatalytic performance can be ascribed to the presence of NiSe2 nanosheets, which facilitate photoinduced electron transfer and offer active sites for the H2 evolution reaction. In addition, a comprehensive analysis of experimental data and density functional theory (DFT) calculations elucidates a plausible mechanism for the enhanced photocatalytic performance. This study provides valuable insights into the development of noble‐metal‐free ZnCdS‐based photocatalysts, a promising candidate for efficient solar‐to‐H2 energy conversion due to their growing prominence in the field.