Liquid-crystalline dimeric molecules consisting of rigid mesogenic cores and flexible oxyethylene spacers have been prepared. The ethoxy carbonyl and alkoxy groups are attached to the ends of the mesogenic cores. These molecules have been complexed with lithium triflate, resulting in thermal stabilization of the mesophases. Ionic conductivities along the direction perpendicular to the molecular director of the smectic A phases have been measured for these complexes.