The aim of the present work is to study the free-radical kinetics of PDMS rubber crosslinking in the presence of 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) nitroxide. For this purpose a new method based on the relationship between the kinetics of the macro-radicals coupling [R-cc(t)] was derived from a fundamental kinetic model and the viscoelastic changes of the complex shear modulus (G'(t)(omega) and G '' (t)(omega)). The kinetic model takes into account the initiator (Dicumyl peroxide in the present study) decomposition and the trapped PDMS macro-radicals in the presence of a radical scavenger such as TEMPO. Activation energy E-ac and collision frequency factor A(0c) for the bimolecular termination reaction coefficient rate k(cc) have been derived from the anisothermal DSC results according to the Kissinger method. Furthermore, it was observed that addition of TEMPO nitroxide can boost the initiator efficiency. The concentration variation of the active PDMS carbon-centred radicals [R-p center dot(t)](act) and the [R-cc(t)] with reaction time were predicted using this kinetic model. On the other hand, the influence of TEMPO concentration in formulation ([N](0)) and effect of temperature on viscoelastic variations are studied. As a main result, the rheological modelling shows that this new method accurately predicts the time variation of complex shear modulus at any temperature and [TEMPO]/[DCP] ratio. (C) 2010 Elsevier Ltd. All rights reserved.