An efficient and simple copper-mediated oxidative coupling of N,N-dimethylanilines with [60]fullerene was employed to obtain a high yield of scarce 6-membered ring [60]fullerene-fused tetrahydroquinolines. The reaction occurred through sp(3) C-H bond activation under mild reaction conditions with molecular oxygen as the oxidant. A plausible reaction pathway was proposed, and the electrochemistry of the fullerene products was investigated.