Copper-based MOF-199 was used as an efficient heterogeneous catalyst to catalyze cross-coupling reactions between N-containing heterocycles and aryliodides with high yields. The catalyst can be easily separated from the reaction mixture, and can be reused at least 5 times without significantly decreasing the activity. The XRD results showed that the crystallinity and structure of MOF-199 can be maintained well during the coupling reaction.