Abstract: | Constructing hollow multi‐shelled structures (HoMSs) has a significant effect on promoting light absorption property of catalysts and enhancing their performance in solar energy conversion applications. A facile hydrothermal method is used to design the SrTiO3?TiO2 heterogeneous HoMSs by hydrothermal crystallization of SrTiO3 on the surface of the TiO2 HoMSs, which will realize a full coverage of SrTiO3 on the TiO2 surface and construct the SrTiO3/TiO2 junctions. The broccoli‐like SrTiO3?TiO2 heterogeneous HoMSs exhibited a fourfold higher overall water splitting performance of 10.6 μmol h?1 for H2 production and 5.1 μmol h?1 for O2 evolution than that of SrTiO3 nanoparticles and the apparent quantum efficiency (AQE) of 8.6 % at 365 nm, which can be mainly attributed to 1) HoMS increased the light absorption ability of the constructed photocatalysts and 2) the SrTiO3?TiO2 junctions boosted the separation efficiency of the photogenerated charge carriers. |