N-Ferrocene (Fc)/porphyrin (Por) [5,6]-open azafulleroids and [6,6]-closed aziridinofullerenes have been synthesized for the first time. Electrochemical measurements revealed that chromophores attached to [5,6]-open azafulleroids are more easily oxidizable than those attached to [6,6]-closed aziridinofullerenes. This was attributed to the delocalization degree of the nitrogen lone-electron pair involved in aziridinofullerene that is larger than that in azafulleroid.