Well-designed hierarchical nanostructures with one dimensional (1D) TiO₂ nanofibers (120–350 nm in diameter and several micrometers in length) and ultrathin hexagonal SnS₂ nanosheets (40–70 nm in lateral size and 4–8 nm in thickness) were successfully synthesized by combining the electrospinning technique (for TiO₂ nanofibers) and a hydrothermal growth method (for SnS₂ nanosheets). The single-crystalline SnS₂ nanosheets with a 2D layered structure were uniformly grown onto the electrospun TiO₂ nanofibers consisted of either anatase (A) phase or anatase–rutile (AR) mixed phase TiO₂ nanoparticles. The definite heterojunction interface between SnS₂ nanosheets and TiO₂ (A or R) nanoparticles were investigated by high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Moreover, the as-prepared SnS₂/TiO₂ hierarchical nanostructures as nanoheterojunction photocatalysts exhibited excellent UV and visible light photocatalytic activities for the degradation of organic dyes (rhodamine B and methyl orange) and phenols (4-nitrophenol), remarkably superior to the TiO₂ nanofibers and the SnS₂ nanosheets, mainly owing to the photoinduced interfacial charge transfer based on the photosynergistic effect of the SnS₂/TiO₂ heterojunction. Significantly, the SnS₂/TiO₂ (AR) hierarchical nanostructures as the tricomponent heterojunction system possessed stronger photocatalytic activity than the bicomponent heterojunction system of SnS₂/TiO₂ (A) hierarchical nanostructures or TiO₂ (AR) nanofibers, which was discussed in terms of the three-way photosynergistic effect between SnS₂, TiO₂ (A) and TiO₂ (R) component in the SnS₂/TiO₂ (AR) heterojunction resulting in the high separation efficiency of photoinduced electron–hole pairs, as evidenced by photoluminescence (PL) and surface photovoltage spectra (SPS).