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, Cu_xO−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.