High performance time-of-flight secondary ion mass spectrometry (TOF-SIMS) characterised by high mass resolution and extreme sensitivity has been applied to the analysis of fullerenes. Optimum emission of secondary ions is obtained from silver substrates covered by approximately one monolayer of fullerene. Besides the intact cluster ions C60+, C70+ and C84+ the positive ion TOF-SIMS spectrum is characterised by peaks which contain silver, oxygen or hydrogen attached to fullerenes (C60Ag+, C70Ag+, (C60)2Ag+, C60O+, C70O+, C60Hn+ and C70Hn+). The spectrum of negative secondary ions shows that negative ion TOF-SIMS exhibits increased sensitivity for large fullerenes such as C84.