Polyaniline (PAn) sensitized nanocrystalline TiO₂ composite photocatalyst (PAn/TiO₂) with high activity and easy separation was facilely prepared by in situ chemical oxidation of aniline from the surfaces of the TiO₂ nanoparticles. The morphology, structure, and light absorption properties of composite photocatalyst were examined in term of its application to photocatalysis. The photocatalytic activity of PAn/TiO₂ nanocomposites for the degradation of methylene blue (MB) aqueous solution was investigated and compared with pure TiO₂. The spectra analyses illustrated that, when PAn deposited on the surface of TiO₂, the crystalline behavior of PAn was hampered and the degree of crystallinity decreased, and the characteristic peaks of the PAn were shifted indicating that there was a strong interaction between PAn and TiO₂ nanoparticles. PAn was able to sensitize TiO₂ efficiently and the composite photocatalyst could be activated by absorbing both the ultraviolet and visible light (λ = 190–800 nm), whereas pure TiO₂ absorbed ultraviolet light only (λ < 400 nm). Photocatalytic experiments showed that under natural light irradiation, MB could be degraded more efficiently on the PAn/TiO₂ than on the pure TiO₂, due to the charge transfer from PAn to TiO₂ and efficient separation of e⁻-h⁺ pairs on the interface of PAn and TiO₂ in the excited state. More significantly, the PAn/TiO₂ composite photocatalyst exhibited easy separation and less deactivation after several runs. The advantages of the obtained PAn/TiO₂ composite photocatalyst revealed its great practical potential in wastewater treatment.