The sulfonation kinetics of the fluoroarylketone chain-end repeat unit of PEEK was studied. To achieve this objective, the sulfonation reactions of a trimer, a tetramer and a polymer, each fluoroarylketone ended, were followed by F-19 NMR. A general kinetic model was developed to determine the kinetic constants from F-19 NMR data. The reliability of the kinetic model and of its mathematical expression was ensured. The kinetic constants are then calculated and discussed. In particular, they were compared with the dimer rate constants previously determined. Lastly and as a conclusion of this work, a general kinetic model describing the sulfonation of main chain repeat units of PEEK is proposed. (C) 2001 Society of Chemical Industry.