Poly[(gamma-methyl-L-glutamate)-co-(gamma-octadecyl-L-glutamate)] with 30 mol % octadecyl units is a "hairy-rod polymer", which provides a highly ordered Langmuir-Blodgett (LB) assembly. Copolyglutamates having a variety of chromophoric moieties (anthracene, naphthalene, and carbazole) in the side chain were synthesized by the copolymerization of the corresponding N-carboxyanhydrides. Their monolayer properties and their structure of the LB him were characterized with respect to the kind and the content of chromophores. Obtained polymers formed stable monomolecular layers at the air/water interface and were transferable onto solid substrates. The CD spectra for the LB films revealed that the polymer chain had an a-helical conformation. Polarized IR spectroscopy showed the preferential orientation of the rodlike main chain to the dipping direction and the random orientation of the chromophore in the side chain. Although the degree of main chain orientation decreased with the chromophore content, chromophores up to 30-40 mol % could be introduced into the copolyglutamates while keeping the order and the structure of the LB film. The LB films of the low-chromophore-content polymers showed only monomer emission in the fluorescence spectra. Excimer formation observed for the higher chromophore content samples was dependent on the kind of chromophore. Obvious excimer emission was observed for the higher naphthalene content films, but the fluorescence spectra of carbazole-labeled LB films showed mainly monomer emission up to 35 mol %. This indicated that the carbazole-labeled LB films had few energy traps such as excimers, resulting in a highly efficient intra- and intermolecular energy migration system.