Polymorphism found in nanofibres of polyamide 6 (PA6) and PA6/clay nanocomposite (PA6-NC), prepared by an electrospinning process, was studied by transmission electron microscopy (TEM) and variable-temperature wide angle X-ray scattering (WAXS), and compared with the polymorphic changes occurring in the pre-electrospun bulk materials. TEM results, concerning morphology and dispersion of the nanoclays, reveal that the produced electrospun nanofibres have an average diameter of 50 nm, and nanoclays are much more uniformly dispersed in the electrospun PA6-NC fibres than in the pristine PA6-NC. According to WAXS measurements, both types of electrospun nanofibres predominantly consist of gamma-form crystals of PA6. Upon heating, from room temperature to the melting point, a number of successive transitions are observed for both systems, namely, crystalline gamma to alpha', alpha' to alpha and alpha to the "amorphous" delta-form due to breakage of hydrogen bonds. On subsequent cooling, it has been observed, for the first time, that the development of crystalline forms for both systems is quite different from each other. The molten electrospun pure PA6 fibres first crystallize in the high temperature alpha'-form, and then they show the room temperature a-form. For these nanofibres, during a temperature cycle of heating and cooling, the initial gamma-form crystals completely turn into the a-form crystals as in bulk PA6. In contrast, for the electrospun nanofibres of the PA6-NC, the gamma-form crystals are preserved after completing a thermal cycle down to room temperature. The present findings on the evolution of polymorphism in the electrospun nanofibres of both systems provide useful information regarding their use as reinforcing elements in polymer composites. (c) 2007 Elsevier Ltd. All rights reserved.