The ring-closing metathesis (RCM) of diethyl diallylmalonate in glycerol micellar conditions was studied using microwave irradiation. The micellization of different cationic surfactants in glycerol was first investigated. The results show the superiority of micellar catalysis in glycerol for a RCM reaction compared to glycerol alone, limiting byproduct formation. In comparison with the classical solution syntheses, the method here described allows safer reaction conditions, less hazardous chemical syntheses, and use of renewable feedstocks. The practical workup, separation, and purification operations minimize the use of materials.