In this work the preparation of polymer electrolyte precursor systems was carried out by means of the physical blending of poly(ethylene oxide) (PEO), a poly(fluoroalcoxi phosphazene) (PPz) and poly(epichlorhydrin) (PECH). The aim was to achieve the compatibilization of the PEO/PPz system over the third component addition. Thermal behaviour study, isothermal crystallization kinetics and spherulitic growth of these binary and ternary blends were conducted with the purpose of gaining insight into the microstructure and the morphology of these materials as a prerequisite for the polymer electrolyte development.