A crystalline porous metal-organic framework Cu3(BTC)2 was synthesized and characterized by several methods including X-ray powder diffraction (PXRD), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic absorption spectrophotometry (AAS), hydrogen temperature-programmed reduction (H2-TPR), and nitrogen physisorption measurements. The Cu3(BTC)2 was used as an efficient catalysts for the direct C−C coupling reaction via cascade methylation and C−H functionalization of N-methylaniline with terminal alkynes for propargylamines synthesis. The catalyst could be easily separated from the reaction mixture by simple filtration, and could be reused several times without a significant degradation in catalytic activity