Small angle X-ray diffraction (SAXS) analysis of blends between nylon 6 and the liquid crystal copolyester Vectra has been performed as a function of composition and thermal treatment in order to make a correlation with the thermal and structural properties of these systems and to get information about their morphological characteristics. Simultaneous small and wide angle X-ray diffraction experiments using synchrotron radiation have been carried out in dynamic experiments to investigate in real time the polymorphic transformations that occur with increasing temperature and the structural changes observed during the melting process.