A new, efficient process has been developed for the preparation of 2,5-unsubstituted pyrrolidino[3',4':1,9]fullerenes by the Ti(O-i-Pr)4-promoted reaction of fullerene C60 with 1,3,5-perhydrotriazines generated in situ upon the reaction of primary alkyl- and benzylamines with paraformaldehyde and EtMgBr.