Novel TiO₂/Sn₃O₄ heterostructure photocatalysts were ingeniously synthesized via a scalable two-step method. The impressive photocatalytic abilities of the TiO₂/Sn₃O₄ sphere nanocomposites were validated by the degradation test of methyl orange and •OH trapping photoluminescence experiments under ultraviolet (UV) and visible light irradiation, respectively. Especially under the visible light, the TiO₂/Sn₃O₄ nanocomposites demonstrated a superb photocatalytic activity, with 81.2% of methyl orange (MO) decomposed at 30 min after irradiation, which greatly exceeded that of the P25 (13.4%), TiO₂ (0.5%) and pure Sn₃O₄ (59.1%) nanostructures. This enhanced photocatalytic performance could be attributed to the mesopore induced by the monodispersed TiO₂ cores that supply sufficient surface areas and accessibility to reactant molecules. This exquisite hetero-architecture facilitates extended UV-visible absorption and efficient photoexcited charge carrier separation.