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Herein, an optimized method for 100 g scale synthesis of glycerol oligomers using a microwave multimode source and the low priced K2CO3 as catalyst is reported. This method allows the complete conversion of glycerol to its oligomers in only 30 min, yielding molecular weights up to 1000 g mol−1. Furthermore, a simple iterative purification process, involving the precipitation of the crude product in acetone and methanol, affords a final product composed of larger oligomers with a narrow dispersity (D < 1.5).