An approach for the creation of a novel family of multi functional crownether-containing comb-shaped copolyacrylates consisting of chromophoric (azobenzene), ionophoric (crown-ether), and mesogenic groups in the same macromolecule was developed. Phase behavior of the copolymers was studied, and correlation between their molecular structure and thermal properties was established. The increase of crown-ether-containing groups' concentration up to 26 mol % leads to disruption of nematic order and formation of amorphous phase. Influence of copolymers complexation with potassium perchlorate on mesomorphic properties of such systems was investigated. It was shown that complexation leads to decrease in mesophase thermostability due to the significant reducing of the side group anisometry by perchlorate counter ion. The comparative investigations of photooptical properties and photoorientation processes of copolymers and their complexes were also performed. An essential difference in kinetics of photooptical behavior was revealed; the bulky crown-ether substituents decrease rotational mobility and prevent photoorientation process of azobenzene fragments diminishing photoinduced orientation and order parameter. (C) 2008 Wiley Periodicals, Inc.