In this study, tendencies of ionization and cleavage processes of time-of-flight (TOF)-SIMS were examined using MS/MS, which enables an easy qualitative analysis of organic matters, to clarify the fragment ions showing structures of the organic materials. In this paper, a result of reviewing fragment ions in TOF-SIMS spectra for polystyrene (PS) as the representative material is shown. Samples were measured with collision induced dissociation (CID)-MS/MS of 1200 L (Varian Inc., USA) and TOF-SIMS J105 (Ionoptika Ltd, UK) for the examination of fragment ions of the PS in TOF-SIMS spectra. The use of CID MS/MS with a wide range of energy distribution is effective for the study of the ionization and cleavage process of TOF-SIMS. As a result, the fragment ions representing the PS structure were clarified, which is useful for the material definition. The qualitative analysis was also applied to the fragment ions particularly obtained in this examination. It is suggested that the examination of the fragmentation process using MS/MS is useful for the mass spectra analysis of organic materials in TOF-SIMS. Copyright © 2014 John Wiley & Sons, Ltd.