<p>In ZnIn₂S₄-based photocatalytic systems, structural optimization and compositional regulation are crucial for significantly enhancing hydrogen production performance. Atom doping and heterostructure formation have been shown to improve solar energy conversion efficiency, thereby boosting photocatalytic performance. However, to date, no one-step synthesis method has been reported that simultaneously constructs hollow heterostructures and introduces heteroatom doping into ZnIn₂S₄ photocatalysts, primarily due to the absence of suitable templates or synthesis strategies. In this study, we propose a novel one-step, coordination-selective strategy based on the hard-soft acid-base theory, using MOF(Ti) as a structure-directing template. By incorporating Ce³⁺, Zn²⁺, In³⁺, and S²⁻, the MOF(Ti) is successfully converted into a hollow MOF(Ce) structure, while Ce-doped ZnIn₂S₄ nanosheets nucleates on its surface. This process yields a highly active 2D/3D hollow core-shell heterojunction photocatalyst, Ce-ZnIn₂S₄/MOF(Ce). Both theoretical and experimental results demonstrate that this unique structure significantly enhances charge separation and extends the charge carrier’s lifetime, leading to markedly improved photocatalytic hydrogen evolution performance. This work offers an innovative and controllable approach for synthesizing MOF-derived hollow core-shell heterojunctions, paving the way for a highly efficient water-splitting system.</p>