End-group characterisation of three functionalised poly(methyl methacrylate) (PMMA) samples was performed by means of matrix-assisted laser desorption/ionisation-mass spectrometry (MALDI-MS). MALDI-time of flight (MALDI-TOF) data were employed to generate information about the initiators and chain-transfer agents used for the polymerisations. Further confirmation of the structural assignments was gleaned from MALDI-collision-induced dissociation (MALDI-CID) experiments. This latter technique is a powerful method for generating information on the masses of individual end groups. (c) 2008 Elsevier Ltd. All rights reserved.