PANI modified core–shell mesoporous TiO 2 (PANI/M-TiO 2 ) with efficient photocatalytic capability under visible light irradiation was fabricated by hydrothermal method and chemisorption approach. The nitrogen adsorption–desorption characterization indicated that the specific surface area of mesoporous M-TiO 2 was 2.8 times as great as that of P25, which resulted in the increased uptake of PANI molecule on the surface of M-TiO 2 . Environmental scanning electron microscopy and transmission electron microscopy images demonstrated that the PANI/M-TiO 2 possessed a unique core–shell structure, which allowed multiple reflection or scattering of light in the photocatalyst and led to the increase of optical path length subsequently. Both the increased uptake of PANI molecules and optical path length in photocatalyst contributed to enhance the visible light absorption. The UV–vis diffuse reflectance spectra confirmed that the optical absorption for PANI/M-TiO 2 was more intensive than that for PANI modified TiO 2 nanoparticle (PANI/NP-TiO 2 ) in the visible light region. The intensive visible light absorption and effective charge separation owing to the heterojunction built between TiO 2 and PANI lead to remarkable improvement of visible light photocatalysis. The pseudo-first-order kinetic constant of photocatalytic degradation of rhodamine B and 4-chlorophenol under visible light irradiation with 6% PANI/M-TiO 2 was 5.04 and 2.03 times as great as that with PANI/NP-TiO 2 respectively, showing the advantage of the unique core–shell mesoporous structure in the PANI/M-TiO 2 for efficient photocatalysis.