Photocatalytic CO2 reduction into syngas (CO and H-2) is one of sustainable strategies for recycling CO2 into value-added products. Herein, a simple and effective two-step self-assembly process was developed to functionalize phosphorescent metal-organic framework (MOF) with single site catalyst. The resulting (Co/Ru).-Ui067(bpydc) supplied molecular platform to enable fast multielectron injection from photosensitizers (PSs) to Co catalyst, leading to the first MOF-based composite photocatalyst for efficient syngas production with a yield of 13,600 mu mol.g(-1) (H-2 : CO = 2 : 1) in 16 h, 29.2-fold higher than that of its homogeneous counterpart. The H-2/ CO ratios can be well controlled by carefully adjusting the molar ratio of PS/catalyst in the MOF platform and the water content in the photocatalytic system. This work provides a prospective strategy for recycling CO2 into H-2-rich syngas by merging PSs and single-site catalysts into a MOF platform.