Methyl 3,4-dihydropyrimidin-2(1H)-one-5-carboxylate derivatives 7 were effectively synthesized on the soluble polymer of polyethylene glycol (PEG) 4000 by heating or solvent-free microwave irradiation through the Biginelli three-component cyclocondensation. Compared with the classical solution-phase Biginelli reactions, the yields could he considerably improved and the reaction lime could he shortened dramatically under microwave promotion in a liquid-phase protocol. Moreover, the polymer-supported synthesis provided the target compounds in high purity.