Three new vanadium oxides were synthesized and characterized using an X-ray. Once incorporated into different polymer systems containing either poly(ethylene oxide) or a poly(ethylene oxide)-polyphosphazene (PPz), together with carbon black (CB) as an electronic crosslinker, kinetic isothermal and nonisothermal crystallization studies were conducted, as well as an electrical characterization study through complex impedance spectroscopy for the purpose of examining, on the one hand, the effects exerted by the different vanadium compounds on the microstructure of the systems into which they are incorporated, and, on the other hand, of determining which of the synthesized vanadium compounds possesses the best conducting properties.