A facile, direct and environmentally benign conversion of C(sp 3 )–H bonds to C(sp 3 )–N bonds using substoichiometric amount of aprotic superelectrophiles polyhalomethane–AlX 3 has been achieved by grinding under solvent-free conditions at room temperature in air. It is a general and simple method for the direct amination of adamantanes, and a series of aminoadamantanes of azoles, arylamines or heteroarylamines were obtained in good to excellent yields. The advantages of this amination are atom economy, solvent-free, chemoselectivity, short reaction time and high yields.