Using biodiesel-based glycerol as raw material to directly synthesize glycerol carbonate with CO₂ can not only promote the benign development of biodiesel industry, but also have positive significance for carbon reduction. However, the glycerol-CO₂ reaction is unfavorable in thermodynamics and kinetics, leading to a poor catalytic property. In order to achieve high activation of glycerol and CO₂, as well as break the low reaction efficiency, accurately and effectively reinforcing the reaction process and tuning the structure of catalysts are of significance. In this survey, we summarize the recent advances of the direct synthesis of glycerol carbonate from carbon dioxide and glycerol in the view of both the catalyst design and the process intensification. Particularly, the thermocatalysis, photothermal catalysis, and electrothermal catalysis are discussed. In addition, the structure–activity relationship and mechanism based on activated glycerol and CO₂ over the heterogeneous catalysts are also presented. Furthermore, we also provide some feasible strategies for catalyst preparation and process intensification to promote the catalytic properties.