In this work we demonstrate one-pot glycidol synthesis, via trans-esterification between glycerol and dimethyl carbonate, by making use of commercially available sodium methoxide as a catalyst. An excellent glycerol conversion (99%) and remarkable glycidol yield (75%) was obtained using dimethyl carbonate/glycerol (molar ratio 2:1) in the presence of 3 wt% catalyst amount (with respect to glycerol weight) at 85 °C for a reaction time of 120 min. Sodium methoxide was recycled and reused twice with only a slight decrease in glycerol conversion. The water content of the glycerol reached 2.5 wt%; this did not reduce the glycerol conversion efficiency of the catalyst. A plausible mechanism for the trans-esterification involved in the preparation of glycidol was proposed.