A novel and highly efficient Cu-catalyzed C-H amination of the monofunctionalized hydrofullerenes for the synthesis of 1,4-difunctional fullerenes has been reported. A new series of 1,4-fullerene derivatives having various monoamine addends were synthesized in good to high yields under mild reaction conditions. The controlled experiments revealed that the reaction proceeds through the formation of a fullerene monoradical as a key intermediate followed by coupling with an amine radical.