1IntroductionThe preparation of highly controlled thin films of lithium ion conducting organic materials is becoming a challenging but rewarding goal in view of obtaining high-performance technological devices like solid-state polymer batteries and capacitors. The classical polymer electrolyte consists of organic macromolecules (usually polyether polymer) that are doped with inorganic (typically lithium) salts. Poly(ethylene oxide) (PEO) is the most commonly employed polymer in PEs because of the peculiar array in the (-CH2-CH2-O-)n chain providing the ability to solvate low-lattice-energy lithium salts. For three decades the major research attention was focused on amorphous polymer electrolytes in the belief that ionic conductivity occurs in a manner somewhat analogous to gas diffusion through polymer membranes. Segmental motion of the polymer chains continuously creates free volume, into which the ions migrate, and this process allows ions to progress across the electrolyte. Such a view was established by a number of experiments, and denied the possibility of ionic conductivity in crystalline polymer phases. This concept has been recently overturned by our group, demonstrating that conductivity comes about as a result of permanent conducting pathways for the movement of ions.