The n-alkyl derivatives C16H33OH, C16H33OCH3, C16H33OC6H5, C12H25OC6H5, (C12H25O)(2)C6H4 or (C16H33O)(2)C=O have been incorporated into the n-alkyl side chain layers formed by the amphiphilic polymer C16O5 and its smectic equimolar complex with LiClO4. All systems have conductivities similar to 10(-2) S cm(-1) at 100 degrees C but the systems with n-alkyls have higher conductivities at lower temperatures (similar to 10(-4) S cm(-1) at 40 degrees C) which are more than two orders of magnitude greater than those of C16O5:LiClO4. This is attributed to the increase in internal space of the ionophilic helical layers brought about by the expanded ionophobic layer. (C) 2000 Elsevier Science Ltd. All rights reserved.