The efficient synthesis of some novel unsymmetrical 1,3-dialkylpyrimidines is described. N3-Alkylation of N1-substituted pyrimidine derivatives with various functionalized alkyl halides in the presence of catalytic amount of tetrabutylammonium bromide (TBAB) and Cs2CO3 in MeCN affords the title compounds. The reactions proceed at room temperature and the products are obtained in good to excellent yields.