The effect of nanoclay on the non-isothermal cure kinetics of polymer layered silicate nanocomposites based upon epoxy resin is studied by calorimetric techniques (DSC and TGA) and by dielectric relaxation spectroscopy (DRS) in non-isothermal cure at constant heating rate. The cure process takes place by homopolymerisation, initiated anionically using 3 wt% dimethylaminopyridine (DMAP), and the influence of the nanoclay content has been analysed. Interesting differences are observed between the nanocomposites with 2 wt% and 5 wt% clay content. At low heating rates, these samples vitrify and then devitrify during the cure. For the sample with 2 wt% clay, the devitrification is accompanied by a thermally initiated homopolymerisation, which can be identified by DRS but not by DSC. The effect of this is to improve the exfoliation of the nanocomposite with 2 wt% clay, as verified by transmission electron microscopy, with a corresponding increase in the glass transition temperature. These observations are interpreted in respect of the nanocomposite preparation method and the cure kinetics. (C) 2012 Elsevier B.V. All rights reserved.