A sector field mass spectrometer was applied to generate fullerene ions with different ionization methods. Electron impact ionisation (EI), chemical ionisation (CI), fast atom bombardment ionization (FAB) and field desorption/field ionisation (FD/FI) were used for the generation of ions. The yield of ions, the molecule fragmentation, multiple ionisation and the detection efficiency of higher and endohedral fullerenes are compared. It was found that the negative ion CI is the best ionisation method for fullerenes. Examples of metallofullerene mass spectra are shown and problems during the recording are discussed. © 1995 Elsevier Science B.V. All rights reserved.