Photocatalytic CO2 conversion to fuel offers an exciting prospect for solar energy storage and transportation thereof. Several photocatalysts have been employed for CO2 photoreduction; the challenge of realizing a low-cost, readily synthesized photocorrosion-stable photocatalytic material that absorbs and successfully utilizes a broad portion of the solar spectrum energy is as yet unmet. Herein, a mesoporous p-type/n-type heterojunction material, CuxO-TiO2 (x = 1, 2), is synthesized via annealing of Cu/Cu2O nanocomposites mixed with a TiO2 precursor (TiCl4). Such an experimental approach in which two materials of diverse bandgaps are coupled provides a simultaneous opportunity for greater light absorption and rapid charge separation because of the intrinsic p-n heterojunction nature of the material. As detailed herein, this heterostructured photocatalyst demonstrates an improved photocatalytic activity. With the CO2 reduction of our optimal sample (augmented light absorption, efficacious charge separation, and mesoporosity) that utilizes no metal cocatalysts, a remarkable methane yield of 221.63 ppm·g-1·h-1 is achieved.