The development of photocatalysts that maximize the utilization of the solar spectrum is crucial to achieving efficient photocatalysis. Herein, the synthesized W18O49@ZnIn2S4 hollow hierarchical structure exhibits superior photothermal-assisted hydrogen (H2) photocatalytic performance under full solar spectrum irradiation. Within this photocatalyst design framework, the use of hollow spherical W18O49 exploits the Localized Surface Plasmon Resonance (LSPR) effect, resulting in increased light absorption. This imparts additional energy to photogenerate carriers through ZnIn2S4, expediting charge migration and elevating the temperature of the reaction system, consequently facilitating the separation of carriers. Notably, the optimized WO(16h)@ZIS-10 sample shows impressive hydrogen evolution rates of 3.11 mmol g−1 under sunlight exposure and 4.98 mmol g−1 h−1 under composite illumination of AM 1.5G and near-infrared (NIR). Additionally, the study explores the impact of different heating methods on photocatalytic activity in solid-liquid reactions, providing valuable insights into effective solar energy conversion through high-activity solar-assisted photocatalysts.