The three-component low-dimensional polymer electrolyte complexes of blends of the amphiphilic helical polymer poly[2,5,8,11,14-pentaoxapentadecamethylene(5-hexadecyloxy-1,3-phenylene)] (I), the block copolymer of poly(tetramethylene oxide)-co-dodecamethylene (II) with LiClO4, LiBF4 and Li(CF3SO2)N have been studied by polarised light optical microscopy, DSC and SAXS together with AC complex impedance measurements using ITO glass, silver and lithium electrodes. In systems with LiClO4 a well-defined spherulitic morphology with lamellae of 1–3 μm in thickness were observed following heat treatment. The lamellae were shown to consist of de-blended polymer I:LiClO4 complex with polymer II forming an interlamellar ion-conducting layer. Complex impedance measurements with ITO and Ag electrodes give σ∼10−3 S cm−1 with low temperature dependence over ambient to 100°C and Z′ versus Z″ planes featuring a new small semicircle on de-blending consistent with a Maxwell series layered dielectric system. A galvanic cell with LiCoO2 composite cathode discharged at 20°C with 0.1 mA cm−2. In corresponding systems with LiBF4, blocks of lamellae separate from a blended matrix which give temperature-dependent AC conductivities. DC polarisation of LiBF4 based systems between Li electrodes give ambient conductivities 10−3–10−2 S cm−1 in good accord with AC impedance measurements. Long spacings from SAXS measurements indicate the I-salt occupancies in blends with the various salts, which correlates to their de-blending tendency.