Benzoin carboxylate derivatives were synthesized with the aromatic aldehydes as raw material in the presence of the catalyst VB 1 . And then, benzoin carboxylate derivatives reacted with different acylating reagents under mild reaction conditions, and benzoin carboxylates were obtained. Further, 2-substituted-4,5-di(aryl)imidazoles were produced from benzoin carboxylates in the presence of solid supports Al 2 O 3 under solvent-free and microware assisted condition, and seven of them have not been reported. The reaction possessed many advantages such as mild reaction conditions, short reaction time, and no organic solvents consumed. Therefore, it is a facile and efficient synthetic method. Moreover, the synthesized compounds were characterized by 1 H NMR, 13 C NMR, IR, HRMS techniques.