Over the last few years polymer electrolytes have generated much interest as potential components in devices such as batteries and smart windows. Some new systems synthesized recently have proven to be excellent candidates for the preparation of thin films, especially Langmuir-Blodgett films. This technique enables the production of single or multimolecular layers of precisely known thickness. The work in this paper concentrates on the investigation of polyether-alkyl bilayer structures and other components utilising the alternate Langmuir-Blodgett technique. We have demonstrated the viability of producing bilayer structures 19 molecular layers (approximately 45 nm) thick. We have also shown that ions can be taken up from the subphase, with conductivity normal to the layer planes being extremely low in contrast to the higher values obtained using bulk Samples. Alkyl chains bearing functional groups are readily blended into the alkyl layers leading to the possibility of creating mixed-function materials. The conductivities of these materials and their blends are discussed.