Our aim in the current work is to focus on a promising and operative method to infuse Co3O4 to a hollow-structured TiO2 sphere. In this work, we synthesized hollow mesostructured TiO2 nanospheres decorated with Co3O4 nanoshells through template-based and sol-gel approaches. The produced photocatalysts are p-n heterojunction Co3O4(shell)@TiO2(core) hollow spheres with a great specific surface area. This mesostructure provides a vast number of photoactive sites for the photocatalytic response. The hexachloroplatinic acid was employed during the photocatalytic action to yield 0.5%Pt/Co3O4(shell)@TiO2(core) composites. The metallic Pt plays the role of transferring the excited electrons. The nanojunction between the p-Co3O4 and n-TiO2 can proficiently prohibit the recombination of photocharges. Consequently, resulting in an outstanding photocatalytic hydrogen production under visible light. The excellent photocatalytic performance was due to the hollow structure, the high specific surface area, and the heterostructure between TiO2 and Co3O4. A reasonable mechanism for the improved photocatalytic efficiency was proposed by facilitating the efficiency of charge carrier transfer at TiO2/Co3O4 interface. This work offers prospective toward the fabrication of high efficient hollow mesoporous photocatalysts for hydrogen production. The procedure used to synthesize the TiO2/Co3O4 nanocomposites is sufficient to create mesoporous mixed oxide photocatalysts for catalysis applications for clean energy applications.