fac-Re(2,2’-bipyridine)(CO)3Cl] (denoted as ReCC) is an efficient molecule-catalyst with high selectivity in the photoreduction of CO2to CO in a homogeneous system. However, the two major drawbacks of Re(I) complexes in the homogeneous system, easy degradation and difficult separation, seriously hinder its development in the field of industrial applications. In this paper, we designed and prepared two different Re-complex fixation systems (denoted as ReCC@TiO2-5 wt% and ReCC-TiO2-5 wt%) based on TiO2gel via the sensitization method and sol–gel method, respectively. Compared with a pure ReCC complex, both of them exhibited excellent photocatalytic reduction activity. In particular, the sol–gel hybrid system (ReCC-TiO2-5 wt%) displayed outstanding positive synergistic effects on the photocatalytic activity and the long durability of the photocatalytic process. A series of characterizations were carried out to explore the probable photocatalytic reduction process mechanism, which provides the theoretical basis and technical support for the Re complex fixation method.