Novel cyclodextrin (CD)-based amphiphilic poly(carboxylic acid)s that self-assemble into highly ordered smectic liquid crystalline mesophases were investigated as a novel class of protonic conductors. These structurally well-defined materials are synthesized from nontoxic and environment-friendly CDs, which possess a unique face-to-face pseudosymmetry. By taking advantage of such geometry, a series of flexible tetraethylene glycol groups terminated with a carboxylic acid functionality were introduced to the CD's secondary face, resulting in the formation of long-range 2D hydrogen-bond networks in the smectic mesophases over a wide temperature window. This new material was found to exhibit impressive proton conductivities in solid states, up to 1.4 × 10-2 S cm-1 at 70 °C and 95% humidity. This constitutes the first report of amphiphilic CD-based liquid crystals applied as proton conductive materials.