An improvement in the photodegradation performance for dyes due to interaction between carbon and titania in a self-assembled mesoporous CTiO2 composite catalyst, even for the difficult degradation of azo dyes, is reported herein. The dye removal process involves adsorption of the dye from water by the mesoporous carbon–titania, followed by photodegradation on the separated dye-loaded solid. Such adsorption–catalysis cycles can be carried out more than 80 times without discernible loss of photocatalytic activity or the anatase content of the composite. In each run, about 120 mg dye per g catalyst can be degraded. The mesoporous carbon–titania catalyst also exhibits a high capacity for converting methyl orange in aqueous solution under visible light. Characterization by XRD, TEM, and N2 sorption techniques has revealed that the self-assembled composite catalyst has an ordered mesostructure, uniform mesopores (4.3 nm), a large pore volume (0.30 cm3 g−1), and a high surface area (348 m2 g−1). The pore walls are composed of amorphous carbon and anatase nanoparticles of size 4.2 nm, which are well dispersed and confined. X-ray photoelectron spectroscopy (XPS), surface photovoltage spectroscopy (SPS), and UV/Vis absorption results indicate doping of carbon into the anatase lattice and a change in the bandgap of the semiconductor. The synergistic improvement in the composite catalyst can be attributed to the following features: (1) carbon doping of the anatase lattice modifies its bandgap and enhances its activity under visible light; (2) confinement within carbon pore walls prevents aggregation of tiny anatase nanoparticles, improving their activity and stability; (3) the mesopores provide a confined space for photocatalysis; and (4) the strong adsorption ability of porous carbon for organic substances ensures that large quantities can be processed and inhibits further diffusion of the adsorbed organic substances, thereby enhancing the mineralization on anatase.