The photocatalysts of immobilized TiO2 film suffer from high carrier recombination loss when compared to its powder form. Although the TiO2 with rutile-anatase mixed phases has higher carrier separation efficiency than those with pure anatase or rutile phase, the single junction of anatase/rutile cannot avoid the recombination of separated carriers at the interface. In this study, we propose a TiO2/SnO2/Ni multi-heterojunction structure which incorporates both Schottky contact and staggered band alignment to reduce the carrier recombination loss. The low carrier recombination rate of TiO2 film in TiO2/SnO2/Ni multi-heterojunction structure was verified by its low photoluminescence intensity. The faster degradation of methylene blue for TiO2/SnO2/Ni multi-junctions than for the other fabricated structures, which means that the TiO2 films grown on the SnO2/Ni/Ti coated glass have a much higher photocatalytic activity than those grown on the blank glass, SnO2-coated and Ni/Ti-coated glasses, demonstrated its higher performance of photogenerated carrier separation.