Polymer blends based on poly(vinylidene fluoride-co-trifluoroethylene) copolymers, P(VDF-TrFE), and poly(ethylene oxide), PEO, with varying compositions have been prepared by solvent casting. In this way, P(VDF-TrFE) crystallizes from the solution while solvent evaporates, while PEO crystallizes from the melt during cooling to room temperature. The surface morphology of the polymer blends indicates the transition from the fibrillar microstructure typical of PVDF-TrFE to the spherulite structure characteristic of PEO. The vibration mode characteristics of P(VDF-TrFE) are not influenced by the presence of PEO in the polymer blend. Confinement of PEO in the P(VDF-TrFE) phase change the conformation of PEO from trans to helix, increasing this transformation for increasing P(VDF-TrFE) content in the polymer blends. Sequential crystallization of the two polymers produce separated amorphous phases whose independent cooperative conformational motions are revealed by two main dynamic-mechanical relaxations. No chemical interaction seems to exist between the polymers within the blend.