The synthesis and characterisation is described of a new liquid crystalline side-chain polymer based on a predominantly poly(ethylene oxide) backbone attached to which via flexible spacers are mesogenic groups. The thermal behaviour and ionic conductivities of this polymer and its complex with LiClO4 are compared to those of a structurally analogous but amorphous polymer. The variation of the ionic conductivity as a function of scaled inverse temperature (T-g/T) differs for the two systems. For the amorphous complex the ionic mobility is coupled to structural relaxations of the polymer and becomes very small at T,. By contrast for the liquid crystalline complex there appears to be a decoupling of the ion motions from structural relaxations. This remarkable observation is thought to imply a new conduction mechanism.