New polymer/ligand complexes could be easily obtained due to the molecular self-assembly of carboxylic acid and hydrogen acceptor fragments through the intermolecular hydrogen-bonding. The polymer/ligand complexes consisting of poly(ethyleneglycol)bis(carboxymethyl)ether (PEOCA), operating as a hydrogen-bonding donor, and pyrazine, 4,4′-bipyridine, or 1,3,5-triazine, serving as a hydrogen-bonding acceptor, exhibited a gel-like structure at room temperature. The high ion conductivity of the order of 10−4–10−6 S cm−1 was achieved for the PEOCA/ligand complexes with LiClO4. The decrease in their conductivity corresponded to the increase in the viscosity and glass transition temperatures of the polymer complexes, but their electrical properties were similar to those of conventional cross-linked PEO polymer electrolytes.