Hierarchically organized mesoporous carbon-TiO2 inverse opal nanostructures were synthesized by complementary colloid and block copolymer (BCP) self-assembly, where the triblock copolymer P123 acts simultaneously as the template and the carbon source. Highly ordered mesoporous inverse opal nanostructures with a nano-textured surface morphology and multiple-length scale nanopores provide increased light-activated surface area and scattering effects, leading to enhanced photoabsorption efficiency and the transport of matter. UV-vis absorption, X-ray photoelectron spectroscopy and Mott-Schottky measurement studies show that incorporation of carbon moieties into TiO2via direct conversion of BCPs creates a new energy level above the valence band of TiO2, resulting in an effective decrease in the band gap. A significantly enhanced visible light photocatalytic activity was demonstrated for the mesoporous carbon-TiO2 inverse opals in terms of the degradation of p-nitrophenol (~79%) and photoelectrochemical water splitting (~0.087%).