A hierarchical self-assembly in comb-shaped supramolecules of conjugated rodlike polymers is reported. The supramolecules consist of poly(2,5-pyridinediyl), aciddopants, and hydrogen bonded alkyl side chains. A thermotropic smectic state with an exceptionally large coherence length is formed without additional solvent. This allows facile overall alignment resulting in high dichroism and polarized photoluminescence. Solid films are formed by cleaving side groups from the supramolecules which retain the optical anisotropy together with the high photoluminescence quantum yield of pristine polymer.