A metal-organic framework Cu2(NDC)2(DABCO) was synthesized and characterized and its properties were examined by several techniques, including X-ray powder diffraction (PXRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), and atomic absorption spectrophotometry (AAS). The Cu2(NDC)2(DABCO) was used as heterogeneous catalyst for the hydroacylation reaction of phenylacetylene and ethyl glyoxalate in the presence of morpholine as base to form 1,2-dicarbonyl-3-ene as principal product. The Cu2(NDC)2(DABCO) exhibited higher catalytic activity in the coupling reaction than that of other MOFs such as Cu3(BTC)2, Cu(BDC), Cu2(BPDC)2(BPY), Cu2(BDC)2(DABCO), Fe3O(BDC)3, In(OH)(BDC), Zr6O4(OH)4(BDC)6, Ni-MOF-74, and homogeneous copper catalysts. The transformation could only proceed to obtain desired product in the presence of Cu2(NDC)2(DABCO). This Cu-MOF could be recovered and reused several times without a significant degradation in catalytic activity.