ZnTiO3–TiO2/organic pillared montmorillonite (pMt) composite catalyst was successfully prepared in this paper by immobilizing ZnTiO3–TiO2 onto pMt. The composition and texture of the prepared composite catalyst were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, energy dispersive spectrometry, ultraviolet–visible light (UV–Vis) diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was tested via photocatalytic degradation of methyl blue (MB) under both visible irradiation and UV light. The results indicated that the ZnTiO3–TiO2/pMt composite catalyst had an apparent absorption at the area of visible irradiation, and exhibited a higher efficiency of photocatalytic degredation of MB under visible irradiation. This was due to the heterostructure of ZnTiO3–TiO2, and the mesoporous structure and specific surface area of the ZnTiO3–TiO2/pMt composite. In addition, the results of the radical scavenging experiments showed that the holes and superoxide radicals are responsible for the degradation of MB under visible irradiation.