The catalytic efficacy of a novel mononuclear rhenium(I) complex in CO2 reduction is remarkable, with a turnover number (TONCO) of 1517 in 3 h, significantly outperforming previous Re(I) catalysts. This complex, synthesized via a substitution reaction on an aromatic ring to form a bromo-bipyridine derivative, L1 = 2-bromo-6-(1H-pyrazol-1-yl)pyridine, and further reacting with [Re(CO)5Cl], results in the facial-tricarbonyl complex [ReL1(CO)3Cl] (1). The light green solid was obtained with an 80% yield and thoroughly characterized using cyclic voltammetry, nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy. Cyclic voltammetry under CO2 atmosphere revealed three distinct redox processes, suggesting the formation of new electroactive compounds. The studies on photoreduction highlighted the ability of the catalyst to reduce CO2, while NMR, FTIR, and electrospray ionization (ESI) mass spectrometry provided insights into the mechanism, revealing the formation of solvent-coordinated complexes and new species under varying conditions. Additionally, computational studies (DFT) were undertaken to better understand the electronic structure and reactivity patterns of 1, focusing on the role of the ligand, the spectroscopic features, and the redox behavior. This comprehensive approach provides insights into the intricate dynamics of CO2 photoreduction, showcasing the potential of Re(I) complexes in catalysis.