Photocatalytic water splitting is a prospective strategy to solve the shortage of human fossil fuel energy. In this work, we designed and synthesized the Pt as co-catalyst decorated on TiO2 nanotubes/metastable zinc-blende (ZB) CdS nanoparticles (NPs) with highly exposed (111) facets (HPTCA3) via the electrospinning-solvothermal and chemical deposition methods. The H2 evolution rate of HPTCA3 was 15025.38 μmol·g−1·h−1, which was about 111.3 and 2.4 times stronger than that of pure CdS power and Pt-TiO2/CdS hollow nanotubes (HPTC). The XRD patterns showed the presence of acetate promoted the growth of ZB CdS (111) crystal facets, and the photogenerated electrons were easily tended to accumulate on the CdS (111) facets, whichwas conducive to the transmission of electrons on the CdS and TiO2 interface. The type II heterojunction can broaden the visible light response range and accelerate the separation and transfer of photo-generated electrons and holes which can be supported by the Optical and Electrochemical characterizations. Band structure calculations and XPS spectrum indicated that the composite catalyst had an efficient electron transfer mechanism, which was beneficial for the spatial separation of photogenerated carriers. The work provides a rational photocatalyst design to improve the performance of photocatalytic splitting of water into hydrogen.