Synthesis of glycerol carbonate from glycerol has gained major research attention because of its wide application in lithium-ion battery and pharmaceutical companies. Current study summarises the catalytic transformation of glycerol-to-glycerol carbonate using MgTiO3 perovskite catalyst. Here,we have reported the synthesis of MgTiO3 catalyst by simple co-precipitation route and investigated the catalytic activity in transesterification of glycerol. The physico-chemical properties of MgTiO3 catalyst was successfully studied by XRD, SEM-EDX, XPS, Raman spectra, BET-surface area and TGA analysis. The designed catalyst possesses high catalytic efficiency and stability in transesterification reaction of glycerol. Depending upon its surface area and basicity many experiments were performed and observed that under optimized condition i.e., 12 wt.% catalyst loading, 6:1 molar ratio of DMC to glycerol, 90 °C and at 180 min highest conversion of glycerol 93% and 88% selectivity of glycerol carbonate was achieved. The reusability study also revealed that MgTiO3 perovskite is highly efficient and stable catalyst to trans esterify glycerol with 88% selectivity towards glycerol carbonate up to sixth cycle.