A highly crystalline porous copper-based metal–organic framework MOF-199 was synthesized from the reaction of 1,3,5-benzenetricarboxylic acid and copper nitrate trihydrate by a solvothermal method. The MOF-199 was characterized by several techniques, including X-ray powder Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermogravimetric Analysis (TGA), Fourier Transform-Infrared (FT-IR), Atomic Absorption Spectrophotometry (AAS), and nitrogen physisorption measurements. The MOF-199 proved to be an efficient catalyst for the C-arylation of aryl iodides with acetylacetone to form α-aryl ketones as the principal products. The catalyst can be separated from the reaction mixture by simple decantation, and be reused without significant degradation in catalytic activity. No contribution from homogeneous catalysis of active species leaching into the liquid phase was detected, confirming that the MOF-199 is a truly heterogeneous catalyst.