Neutral and anionic C60(CN)2 were investigated with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectrometry. It was observed that its anions underwent cyano- group and oxygen transfer, and dimerization processes in ESI conditions to form C60(CN)3H−, C60(CN)2(OH2)−, [C60(CN)3H]− 2, [C60(CN)2(OH2)]− 2 and [(C60)2(CN)2(OH)]−. Meanwhile, neutral C60(CN)2, for which no signal was observed in ESIMS, showed a base peak corresponding to C60(CN)2Cl− in APCIMS spectra with CHCl3 used as solvent, while only a molecular ion peak corresponding to C60(CN)− 2 was observed for the toluene solution of neutral C60(CN)2 in the same conditions. Possible mechanisms for group transfer and dimerization were proposed based on these observations.