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A novel MnO 2 /g-C 3 N 4 heterojunction composite was synthesized via a simple in-situ redox reaction between KMnO 4 and MnSO 4 ·H 2 O adsorbed on the surface of g-C 3 N 4 for the first time. MnO 2 featuring 2D δ-phase layered structure was intimately attached onto the surface of g-C 3 N 4 layers via C O bonding. Notably, the synthesized MnO 2 /g-C 3 N 4 photocatalyst showed substantially enhanced photocatalytic activity in the reduction of CO 2 than pure g-C 3 N 4 and MnO 2 . The highest CO production amount of 9.6 μmol g −1 has been obtained at an optimized loading amount of MnO 2 under 1 h irradiation of a 300 W Xe lamp. The incorporation of narrow band gap MnO 2 on the surface of g-C 3 N 4 enhanced its light harvesting ability. And the solid hetero-interface between MnO 2 and g-C 3 N 4 together with their well matched band structure was favorable for the separation of photo-induced carriers, consequently enhanced its photocatalytic activity. This novel 2D-2D MnO 2 /g-C 3 N 4 heterostructure is expected to have great potentials in CO 2 photoreduction. [ABSTRACT FROM AUTHOR]