The cycloaddition of CO2 and propylene oxide (PO) is of great significance to green chemistry and resource utilization. Here, two new metal clusters and four ruthenium photosensitizers were synthesized, and a series of composite catalysts were prepared by combining them with cobalt phthalocyanine. Light was introduced into the reaction system and it was found that TON increased from 550 (0 W) to 990 (200 W) at 60 °C. At 120 °C, 200 W, the TON was as high as 4616. The electron paramagnetic resonance (EPR) experiments showed that for the Cat13, electrons were generated by light irradiation. After the system was injected into PO, the photogenerated electrons quickly transferred to PO. Gibbs free energy calculations also indicate that by introducing light, the system is more likely to promote PO ring opening and exhibits excellent catalytic performance for CO2 ring addition. In addition, the recycled catalyst can still catalyze the formation of propylene carbonate from CO2 and PO.