Polymers having the structurewhere R = -C16H33 Or -C12H25 and n = 5 or 6 (coded C1605 etc.) have been synthesised. Complexes with several salts of Li, Na and Mg have been prepared, eg C1605-LiClO4 (1:1) where numbers in parenthesis denote the molar proportions of repeating unit to salt. Using thermal analysis, polarised light microscopy, SAXS and WAXS techniques and energy minimised modelling it is shown that the complexes having 0.5 to 1.0 mol salt per polymer repeating unit form smectic liquid crystal structures above the sidechain melting temperatures leg 43.5 degrees C for C1605-LiClO4 (1:1)). The salt is complexed to the two-dimensional helical polyether backbone layers which are separated by hydrocarbon layers. Both sheared and unsheared samples are compared. In contrast to expectation from conventional polymer electrolyte behaviour, the ionic conductivities of the lithium salt complexes in the liquid-crystal phases are greatest for systems having the most extensive organisation following the sequence C1605 > C1606 > C1206 and the sheared samples are the more conductive. The lithium salt complexes in general have the highest conductivities though Na and Mg complexes are similarly organised and lower conductivities are ascribed to lower cation mobilities.