Sodium-conducting solvent-free polymer electrolytes based on commercially available and inexpensive materials poly(oxyethylene), POE, and three different sodium salts (NaI, NaCF3SO3 and NaClO4) were prepared and exhaustively characterized. In order to minimize the environmental impact related to conventional film processing based on casting, a combination of lyophilization and hot-pressing was successfully applied. Contrary to film-casting, this new approach led to very homogeneous and pore-free films. This study suggests the obtained polymer electrolyte films as a promising route to enhance not only ionic conductivity but also mechanical properties. Furthermore, a preliminary work on salt blends hosted by POE shows that they strongly decrease melting point and crystallinity of the polymer electrolytes and paves the way for enhanced sodium-conducting materials.