Visible-light responsive TiO2-V2O5 catalyst was prepared using a binary sol-gel and in-situ intercalation method.The TiO2 sol and V2O5 sol were mixed to disperse the V2O5 species in the TiO2 phase at molecular level. The binary sol was then intercalated into interspaces of polyaniline (PANI) by means of in-situ polymerization of aniline. Conglomeration of the TiO2-V2O5 clusters during the calcination process was avoided because of the wrap of polyaniline. The surface morphology, the crystal phases, the stmcture, and the absorption spectra of (PANI)n/TiO2-V2O5 and the composite catalyst were studied using SEM, XRD, FI-IR, and UV-Vis. The photoactivity of the prepared catalyst under UV and visible light irradiation were evaluated by decolorization of methylene blue (MB) solution. The results showed that the composite catalyst displayed a homogeneous anatase phase, and the vanadium pentoxide species was highly dispersed in the TiO2 phase. The composite catalyst responded to visible light because of the narrowed band gap. In this study, the catalyst with the sol volume ratio of TiO2: V2O5 = 10:1 presented the best photocatalytic activity.