Constructing a hollow porous ZnO-ZnS sphere is still a big challenge due to the difficulty in controlling the morphology and distribution of ZnO shell originating from the fact that ZnO prefers to grow along particular crystal planes. Here, we demonstrate a novel synthetic strategy for the preparation of oxygen-vacancy-enriched ZnO-ZnS hollow porous (Ov-ZOS (HP)) spheres by combining the concepts of adopting a template-directed method, selecting the sulfidation precursor, and tuning the calcination process of the template. Structural characterization and density functional theory (DFT) calculations reveal that hollow porous nanostructures and oxygen vacancies in the ZnO-ZnS heterojunction are beneficial in promoting efficient charge transfer and separation. The optimized Ov-ZOS (HP) exhibits enhanced rates of hydrogen evolution reaction (71.86 mmol h