Polystyrene-supported, metal containing imidazolium salt [PS-(Im)(2)MX2] catalysts were prepared and characterized by various analytical methods, and their role in the synthesis of glycerol carbonate from glycerol and urea was investigated under mild conditions. Among different metal containing PS(Im)(2)MBr2 catalysts, the yield of GC increased Cu < Mg < Zn, which is the order of acid-base balance of the catalysts. PS-(Im)(2)ZnI2 catalyst, which showed a good balance of the acid-base properties, was the most active and selective catalyst: it was readily recoverable and reusable in the subsequent reaction cycles. Furthermore, the reaction pathway for the glycerolysis of urea was studied with the time-on-line analysis of the products via a combination of FT-IR spectroscopy and C-13 NMR analysis. The effects of reaction parameters such as temperature, degree of vacuum, catalyst loading, and the ratio of reactants on the reactivity were also investigated to elucidate the reaction mechanism. (C) 2014 Elsevier B.V. All rights reserved.