Liquid-crystalline side-chain polymeric complexes with well-defined structures have been obtained by supramolecular assembly of poly(acrylic acid) and mesogenic compounds containing imidazolyl-terminated alkyl chains. Hydrogen bonds formed between carboxylic acid and N-(alkyl)imidazole moieties can function as molecular connectors. The formation of R-bonded liquid-crystalline networks has been achieved by self-assembly of bis-imidazolyl-terminated mesogenic compounds and poly(acrylic acid). These networks exhibit smectic A phases due to the dynamic nature of the noncovalent interaction.