The smallest hydro-[60]fullerene, C60H2, has been studied by matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry. The ionisation of C60H2 was accomplished for the first time free of unwanted dissociations in electron transfer reactions with cations derived from the DCTB matrix. The findings pave the way to the use of MALDI for the quantitation of lower hydrofullerenes or investigations into the release of hydrogen. Direct LDI and negative-ion MALDI are less suited for a meaningful analysis. However, negative-ion MALDI reveals that C60H2 degrades through oxidation. (C) 2010 Elsevier B.V. All rights reserved.