A Ziegler-Natta catalyst system (TiCl4-MgCl2/magnesium chloride-methanol adduct) was efficiently found to catalyze the three component Biginelli reaction of an aldehyde, beta-keto ester, and urea or thiourea under solvent free conditions to afford the corresponding 3,4-dihydropyrimidin-2-(1 H)-ones in excellent yields. The enhanced surface areas of TiCl4-MgCl2 -methanol adduct plays significant role in providing an efficient synthesis of Biginelli compounds. (c) 2007 Elsevier B.V. All rights reserved.