A process for the production of glycerol carbonate (GC) is proposed with the transesterification of glycerol (GL) and dimethyl carbonate (DMC) with CaO as catalyst by reactive distillation and extractive distillation. The performance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimentally. The results indicate that both the GL conversion and GC yield increase with the DMC/GL molar ratio, reflux ratio, final temperature of tower bottom, and CaO/GL molar ratio and decrease as the recycle number of CaO increases. The calcium concentration in the residual reaction mixture also decreases remarkably as the DMC/GL molar ratio increases. At DMC/GL molar ratio 4.0, reflux ratio 1.0, final temperature of tower bottom 358 K, and CaO/GL molar ratio 0.05, both the GL conversion and GC yield can reach above 99.0%, and the mass concentration of calcium in the product is less than 0.08%. (C) 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.