AbstractIonic conductivities of complexes of polystyrene derivatives having a spacer, CH2O(CH2CH2O)n (poly‐(SEDEP), n = 1; poly(SDEDEP), n = 2), between backbone and pendant penta(methoxyethoxyethoxy)cyclotriphosphazene with LiClO4were investigated as functions of temperature and salt concentration. The glass transition of temperature of poly(SEDEP) and poly(SDEDEP) was observed at −64 and −65°C, respectively. The extent of Tgelevation of the Li+–polymer complexes was not affected by the difference of spacer in the host polymers. The conductivities of the complexes exhibit non‐Arrhenius temperature dependence. The conductivities of poly(SDEDEP)–Li+complexes were somewhat higher than those of poly(SEDEP) systems and the maximum value close to 10−4S/cm at 50°C has been achieved at [Li+]/O = 0.08. The results are compared with those obtained previously for the complexes based on polymers which have the similar structures but no spacer, and the correlation between the conduction mechanism and polymer character