Covalent organic framework (COF) represents an emerging class of porous materials that have exhibited great potential in various applications, particularly in catalysis. In this work, we report a newly designed 2D COF with incorporated Re complex, which exhibits intrinsic light absorption and charge separation (CS) properties. We show that this hybrid catalyst can efficiently reduce CO2 to form CO under visible light illumination with high electivity (98%) and better activity than its homogeneous Re counterpart. More importantly, using advanced transient optical and X-ray absorption spectroscopy and in situ diffuse reflectance spectroscopy, we unraveled three key intermediates that are responsible for CS, the induction period, and rate limiting step in catalysis. This work not only demonstrates the potential of COFs as next generation photocatalysts for solar fuel conversion but also provide unprecedented insight into the mechanistic origins for light-driven CO2 reduction.