The copper-catalyzed versatile C(sp²)–C(sp³) bond formation with N-heteroaromatics and hydrogen donors was developed. Various alkanes and ethers reacted with quinolines, isoquinolins, pyridines, benzooxazole and benzothiazole to give the corresponding C(sp²)–H alkylation products via cross-dehydrogenative coupling. On the other hand, we achieved the high regioselective C(sp²)–halogen alkylation of (hetero)aryl chlorides and (hetero)aryl bromides with ethers via elimination of the halogen radical. The reaction mechanism was investigated with control experiments.