A discotic liquid crystal triblock copolymer consisting of a central main chain triphenylene-based liquid crystal block capped at both ends by blocks of poly(ethylene oxide) (PEO) (M W =2000gmol−1) has been doped with lithium perchlorate in an EO:Li 6:1 ratio. The polymer electrolyte exhibits a phase separated morphology consisting of a columnar hexagonal liquid crystal phase and PEO-rich regions. The polymer electrolyte forms self-supporting, solid-like films. The ionic conductivity on initial heating of the sample is very low below ca. 60°C but increases rapidly above this temperature. This is attributed to the melting of crystalline PEO-rich regions. Crystallisation is suppressed on cooling, and subsequent heating cycles exhibit higher conductivities but still less than those measured for the corresponding lithium perchlorate complex in poly(ethylene glycol) (M W =2000gmol−1). Instead the triblock copolymer mimics the behaviour of high molecular weight poly(ethylene oxide) (M W =300,000gmol−1). This is attributed, in part, to the anchoring of the short PEG chains to the liquid crystal block which prevents their diffusion through the sample. Temperature and pressure variations in ion mobility indicate that the ion transport mechanism in the new material is closely related to that in the conventional PEO-based electrolyte, opening up the possibility of engineering enhanced conductivities in future.