A new diol with azoaromatic pendant was prepared by N-phenyl-4-amido-3,4-dichloromaleimide with 2-mercaptoethanol in the presence of NaOH, and used to obtain photosensible poly(urethane-urea) varnish. A poly(urethane-urea) varnish bearing azobenzene chromophores, based on a poly(ethylene adipate)diol (average molecular weight-2000), 4,4'-dibenzyldiisocyanate, diethylene glycol, trimethylolpropane, and afore-mentioned diol, were prepared and characterized. The polymers were characterized by FTIR spectroscopy, thermal analysis (DMA, DSC, and TGA), and the photochromic behavior by UV irradiation of thin films was discussed.