Versatile decarboxylative C–H alkylation of heteroarenes was accomplished. In the presence of Cu(OTf)₂ and 4,4′-di-tert-butyl-2,2′-bipyridine, a range of heteroarenes, such as imidazo[1,2-a]pyridines, 2-phenylbenzo[d]imidazo[2,1-b]thiazole, 2-phenylindolizine and 4H-chromen-4-one, can be alkylated using diverse alkyl carboxylic acids. This developed protocol will extend the still limited number of copper catalytic decarboxylation couplings, especially in the construction of C_sp²–C_sp³ bonds.