Semiconductor-based photocatalyst serves as an attractive candidate for harnessing solar energy to generate renewable hydrogen via water splitting. Here, a novel Au/SrTiO3/TiO2 (T3) photocatalyst of 3D SrTiO3/TiO2 hollow nanosphere decorated by plasmonic Au nanoparticle (NP) is precisely constructed via an in-situ growth of cubic SrTiO3 on anatase TiO2 hollow nanospheres. By carefully regulating the SrTiO3/TiO2 interface structure, the optimized Au/SrTiO3/TiO2 (T3) photocatalyst achieves a remarkable photocatalytic H2 evolution rate of 327.8 μmol g−1 h−1 without Pt as cocatalyst. Specifically, spectroscopic analyses and characterization results comprehensively prove that the favorable plasma electric field (Au) and the internal electric field (SrTiO3/TiO2 heterojunction) coupled with the 3D electron transfer channel in 3D Au-SrTiO3/TiO2 hollow nanospheres synergistically promote the interfacial charge separation and accelerate the interfacial transfer of charge carriers for efficient solar-driven photocatalytic H2 evolution. This work presents a new strategy for the rational design of plasmonic metal functionalized 3D heterojunction photocatalysts for highly efficient solar-to-chemical energy conversion.