AbstractBACKROUND: One of the most important properties of the azobenzene chromophores is the photochemical trans–cis isomerization induced by UV or visible light. In azopolymers, the photoisomerization induces conformational changes in the polymer chains, which in turn lead to macroscopic variations in the chemical and physical properties of the surroundings and media.RESULTS: This work reports the photochromic behaviour and surface structuring capacity of azopolymers having rigid polyimide and flexible polysiloxane structures, respectively. These polymers have good thermostabilities, with the degradation process starting above 315 °C. The glass transition temperature of the azopolyimide is 228 °C, while that of the azopolysiloxane modified with thymine is 34 °C.CONCLUSION: The experiments show that the azobenzene groups can isomerize even in the case of the rigid polyimide, but the maximum degree of conversion to the cis isomer is less than in the case of the flexible polysiloxane. This behaviour is reversed in solution, probably due to both the thymine and azo group interactions and for conformational reasons. The azopolymers show a good surface structuring capacity. The polysiloxane is more sensitive in the case of low irradiation energy and irradiation time. By increasing the irradiation time for both polymers, the modulation depth increases and has comparable values. Copyright © 2008 Society of Chemical Industry