The valorization of glycerol has been a focal point of research, with one promising approach being the synthesis of glycerol carbonate via the glycerol carbonylation reaction. The main challenge in this process lies in the design of efficient catalysts. In this study, we investigated various transition metal-derived ZIF (Zeolitic Imidazolate Framework) materials as catalysts, including ZIF-8, ZIF-67, Cu-ZIF, Cu-ZIF-8, Cu-ZIF-67, and Co-ZIF-8. Our findings revealed a significant improvement in catalytic activity under bimetallic conditions. The underlying reasons for this enhancement were further explored through computational simulations, which attributed the effect to changes in natural charge distribution. Additionally, the influence of calcination temperature on catalytic performance was extensively studied. We observed that copper-containing ZIF materials exhibited unique catalytic properties at different calcination temperatures, with activity following a trend of initially decreasing, then increasing, followed by a decrease, and finally increasing again with further temperature rise. A deeper investigation into this phenomenon revealed that at high temperatures (≥800°C), copper synergized more effectively with palladium, leading to an enhancement in catalytic activity.