Azobenzene-containing poly(amic acid)s and resulting polyimides were synthesized. Polymers differed in the polymer backbone structure and the position at which the azobenzene group was attached to the polymer chain. Polymers were characterized and evaluated using Fourier transform infrared, 1 H NMR and UV-visible spectroscopies, X-ray diffraction, differential scanning calorimetry (DSC) and thermogravimetric analysis. Polyimides revealed glass transition temperatures in the range 160-265 ∘ C, and thermal stability with decomposition temperatures in the range 336-444 ∘ C. The thermal imidization kinetics of poly(amic acid)s was investigated by means of DSC. Kinetic parameters, such as the activation energy (E) and the frequency factor, were estimated using the Ozawa and Kissinger models. The values of E, determined using both methods, were in the range 142.52-200.92 kJ mol −1 . The photoinduced optical anisotropy (POA) was studied in the obtained azopolymers using a holographic grating recording technique. Surface relief gratings, which appeared after light exposure, were observed using atomic force microscopy. For the first time to the best of our knowledge, photoinduced anisotropy in poly(amic acid)s was studied and compared with POA in their polyimide analogues.