AbstractWe report on directed self-assembly in supramolecules containing rod-like polymers. The comb-shaped supramolecules consist of poly(2,5-pyridinediyl), camphorsulfonic acid, and hydrogen bonded amphiphilic side chains. Locally they form highly ordered lamellar structures in which the polymers are stacked. The liquid crystalline state allows facile overall alignment yielding absorption dichroism and polarized photoluminescence. After alignment, cleavage of the amphiphiles results in solid films which retain this optical anisotropy with the high photoluminescence quantum yield.