The product, 2-phenyloxazolo[3,2-a]benzimidazole was synthesized by three steps. Firstly, 2-bromo-1H-benzo[d]imidazole was obtained after1H-benzo[d]imidazole -2-thiol was brominated. Then 2-bromo-1H-benzo[d]imidazole reacted with 2-bromo-1-phenyl-ethanone, the intermediat was gotten. At last, 2-Phenyloxazolo[3,2-a]benzimidazole was synthesized by copper-catalyzed cyclization. We investigated the influence of the solvents, bases, ligands on the Coupling cyclization of 2-Phenyloxazolo[3,2-a]benzimidazole.