Hollow Multishelled Structured SrTiO ₃ with La/Rh Co‐Doping for Enhanced Photocatalytic Water Splitting under Visible Light

La‐ and Rh‐co‐doped SrTiO 3 (STO:La/Rh) hollow multishelled structures (HoMSs) are fabricated by adding La 3+ and Rh 3+ ions during the hydrothermal process of converting TiO 2 HoMSs to STO HoMSs. STO:La/Rh HoMSs have successfully expanded the light absorption edge to 520 nm. Accompanied with the benefits of the unique hierarchical structure and relatively thin shells, STO:La/Rh HoMSs exhibit elevated light‐harvesting capacity and charge separation efficiency. Compared with STO:La/Rh nanoparticles (NPs), STO:La/Rh HoMSs demonstrate enhanced photocurrent response, photocatalytic hydrogen evolution activity, and the quantum efficiency. Moreover, overall water splitting is realized by a Z ‐scheme system combining STO:La/Rh HoMSs with BiVO 4 (BVO) nanosheets with 1 wt% Pt as the co‐catalyst. Steady evolution of hydrogen and oxygen is performed under both visible light and simulated sunlight irradiation. The solar‐to‐hydrogen efficiency of double‐shelled STO:La/Rh HoMS–BVO photocatalysts reaches 0.08%, which is twofold higher than STO:La/Rh NP–BVO photocatalysts.