Polyazothiophene is a type of polythiophene derivative that combines the electrical and luminescent properties of polythiophenes with the photoisomerization property of azopolymers. Extensive efforts have been made to improve the properties of polyazothiophenes, such as Solubility, optical, and chromic properties. We report the preparation of copolymers of an alkylthiophene (3-octylthiophene, 3-OT) and an azothiophene (2-[N-ethyl-N-[4-[(4-(4-nitrophenyl)azolphenyl]amino]ethyl 3-thienylacetate, 3-AzoT) in different ratios as an alternative route to improve these properties. The azosubstituted monomer contents in these copolymers were 6, 9, 12, and 51% (in mol), as evaluated by elemental analysis. Their chemical structures were confirmed by FTIR and H-1-NMR. HPSEC and thermal analysis were used to characterize the polymers. The presence of thermochromic and solvatochromic properties was demonstrated by UV-Vis spectroscopy. Optically induced birefringence was detected only in polymers with 12 and 51 mol % of azo-units. The introduction of different ratios of the azothiophene in the copolymer alters the polymer solubility and emissive properties. The results indicate that the polyazothiophene copolymers presented are promising active layers for optical devices and sensors. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 680-687, 2009