A series of novel bis-2-phenylpyrimidines with alkyl linkages have been prepared by a three-component cyclo-condensation of benzamidine hydrochloride, β-ketoester, and dihaloalkanes. The easy work-up of the products, rapid reaction, and mild conditions are notable features of this protocol. The reaction was efficiently catalyzed in one-pot by K2CO3 as a base in N,N-dimethylformamide under optimized temperature (70 °C) conditions providing the title compounds in moderate to high yields. The antibacterial activities of the selected products were evaluated against some strains of Gram-positive and Gram-negative bacteria. Biological data indicated that some products exhibit promising activities.