A crystalline copper-based metal–organic framework Cu/MOF-74 was synthesized, and used as an efficient heterogeneous catalyst for the synthesis of 1,2-dicarbonyl-3-enes by means of the hydroacylation of 1-alkynes with glyoxal derivatives in the presence of a base. Cu/MOF-74 was found to be more catalytically active for the synthesis of 1,2-dicarbonyl-3-enes than other MOFs including Cu2(BDC)2(DABCO), Cu3(BTC)2, Cu(BDC), Cu2(NDC)2(DABCO), Cu4I4(DABCO)2, Ni-MOF-74, Zn-MOF-74, Fe3O(BDC)3, In(OH)(BDC), and Zr6O4(OH)4(BDC)6. Cu/MOF-74 also exhibited better performance than other homogeneous copper catalysts, including Cu(OAc)2, Cu(NO3)2, CuI, CuBr, CuCl,CuCl2, and CuBr2. The Cu/MOF catalyst was able to be recovered and reused several times without a significant degradation in catalytic activity. To the best of our knowledge, the formation of 1,2-dicarbonyl-3-enes has not previously been carried out under heterogeneous catalysis conditions.