Abstract: The progresses on mass spectrometry studies of fullerenes and their derivatives in the past twenty years have been reviewed. Various applications of laser desorption time-of-flight mass spectrometry (LD-TOFMS), chemical ionization mass spectrometry (CIMS), desorption chemical ionization mass spectrometry (DCIMS), desorption electron impact mass spectrometry (DEIMS), electrospary ionization mass spectrometry (ESIMS) and fourier transformation-ion cyclotron resonance mass spectrometry (FT-ICRMS) on the characterizations, formation mechanism and structures of fullerenes were summarized. Be-cause fullerenes are difficult to be volatilized and capable of absorbing the UV radiation, LDMS is specially suitable for fullerenes analysis. Combined with other techniques, LDMS also provided large quantity of information about the formation mechanism and conformation of fullerenes. The desorptions as well as ion/molecule reactions of fullerenes were also studied by various mass spectrometry techniques.