Novel azosystems possessing chemical architecture that allows for noncovalent attachment of the azobenzene or azopyridine chromophores to poly(ester imide) matrix via hydrogen bonding were fabricated. Chosen physicochemical properties including the ability of the chromophores to realign upon linearly polarized light were determined and discussed in relation to details of the materials structure. Calculations based on density functional theory (DFT) were employed to understand and explain a structural reason affecting hydrogen bond formation ability and photoresponsive behavior of the studied azosystems. For the first time, the Fox equation was shown to be applicable for calculating the glass transition temperature of hydrogen-bonded azopolymers. Moreover, it was demonstrated that azopyridine polymers may exhibit a very efficient molecular photo-orientation provided that they possess a proper structural design. (C) 2017 Elsevier Ltd. All rights reserved.