A series of polyurethane elastomers containing aromatic azobenzene chromophore in the hard segment was synthesized by a one-step method. AFM surface study showed that particles on the order of 100 nm to several micrometers appeared after annealing the polymer films. Birefringence was induced in these polymer elastomers. The stability of the photoinduced birefringence could be improved significantly by annealing the polymer films. This also induced microphase separation. The effects of azo contents and molecular weight of soft segments were investigated. Dynamic study shows that photo-inducing rate decreased while relaxation rate increased after annealing. Surface relief gratings could be induced only on the pure polyurethane and the elastomer containing 75% bis(azo)-diol. Only a reversible volume hologram was observed for the other elastomers.