The tridentate ligand 2,4,6-tris(2-(pyridin-4-yl)vinyl)-1,3,5-triazine (TPVT) was designed and synthesized. We prepared metal-organic framework (TPVT-MOFs) crystals containing TPVT, 1,3,5-benzenetricarboxylic acid and cobalt by solvothermal reaction. Then, a series of composite materials with different contents of TPVT-MOFs were obtained by combining TPVT-MOFs with g-C3N4. Due to the interaction between TPVT-MOFs and g-C3N4, the composite materials have a more favorable valence band (VB) and conduction band (CB) for photocatalytic reduction of CO2 and oxidation of H2O. Under the conditions of visible light and a gas-solid system without a co-catalyst, a photosensitizer and a sacrificial agent, the yield of CO2 reduction by TPVT-MOFs@g-C3N4-10 can reach 56.4 μmol·g-1·h-1, which is 3.2 times that of pure g-C3N4 (17.5 μmol·g-1·h-1). The results of DFT calculations showed that the adsorption of H2O on the TPVT-MOFs@g-C3N4 composite material was more preferential, which promoted the adsorption and reduction of CO2.