The development of molecular composite photocatalysts for cost-effective, sacrificial-reagent-free CO2 reduction is desirable but challenging. Herein, we employed an in situ encapsulation strategy to encapsulate the binuclear cobalt complex (Co2L) within NH2-MIL-125 and synthesized a range of MOF-based composites with varying cobalt content for photocatalytic CO2 reduction. The photocatalytic results showed that the catalytic performance increased with the increase in Co2L content, reaching a rapid CO generation rate of 27.95 μmol·g-1·h-1, over 5 times that of bare NH2-MIL-125, with water as the electron donor instead of any organic sacrificial agent. This composite catalyst effectively harnesses the advantages of both molecular catalysts and MOFs, leveraging the superior catalytic activity of molecular catalysts while also capitalizing on the light absorption and water oxidation capabilities of MOFs, resulting in a remarkable ability for photocatalytic CO2 reduction. The photocatalytic mechanism involving electron transfer and CO2 activation has been revealed by photoluminescence spectroscopy, in situ X-ray photoelectron spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, and other control experiments.