A crystalline metal-organic framework Cu-CPO-27 (also known as Cu-MOF-74) was synthesized and characterized by several methods including X-ray powder diffraction (PXRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The Cu-CPO-27 was used as an efficient catalyst for the synthesis of 2-arylquinazolinones via ring expansion reaction of 2-arylindoles with amines to form 3-phenethyl-2-phenylquinazolin-4(3H)-one as the desired product. The copper-catalyzed reaction could proceed readily, with more than 94% reaction yield being achieved after 24 h at 80oC in the presence of 7.5 mol% Cu-CPO-27 catalyst. This material exhibited higher catalytic activity in the coupling reaction than that of other MOFs such as Cu(BDC), Cu(OBA),Co2(dhtp), and homogeneous copper catalysts. The transformation could only proceed to obtain major product in the presence of the Cu-MOF. It was possible to recover the Cu-CPO-27 catalyst by simple filtration separation, and reutilize them for the reaction without a significant decline in catalytic efficiency.