A family of self-assembling LC columnar polyethers were prepared by chemical modification of linear polyglycidol with a polymerization degree equal to 20, with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoic acid by Steglich esterification. The modification degrees of the resulting LC polyethers ranged between 8 and 43%. All the obtained copolymers exhibited LC behavior and the higher the modification degree, the higher the clearing range, as expected. Mesophase self-assembling depended on the amount of dendrons introduced: in the case of modification degree ranging around 10%, the copolymers exhibited lamellar columnar structure, while for the highest modification degrees, hexagonal columnar mesophase resulted; in the case of intermediate degree of modification, the copolymers exhibited a rectangular columnar mesophase. Oriented membranes could be prepared from modified polyglycidol with different modification degrees and showed promising proton permeability values. Therefore, these materials are proposed as interesting candidates for proton transport materials. (C) 2015 Elsevier Ltd. All rights reserved.