The approach of deriving new photooptically active polymeric substances by hydrogen bonding between functionalized liquid crystalline (LC) copolymers and low-molecular-mass dopants, containing photochromic azobenzene fragments, is described. The formation of intermolecular hydrogen bonds between carboxylic groups of functionalized LC copolymers and the pyridine fragment of the dopant leads to stable, nonseparating mixtures in a broad interval of contents (up to 30 mol % dopant molecules). The phase behavior and structure of photochromic mixtures are investigated. Induction of a nematic mesophase is observed in the case of a smectic polymer matrix doped with low-molar-mass photochromic dyes.