Abstract.We report the reversible micro-structuring of a synthetic rubber polymer (cis1,4-polybutadiene (PB)) by femtosecond laser illumination. Visco-elastic relaxation of the optically damaged region was observed. The recovery time, typically 102–104 ms, can be varied by changing the irradiation pulse energy. Multi-shot-induced damage recovers on the much longer scale of 101–102 s. It was found that the doping of PB by 4 wt. % of pentazadiene ([4-NO2]–phenyl–N=N–N(C3H7)–N=N–phenyl–[4-NO2]) reduces the threshold of light-induced photo-modification by 20%. This is explained by photo-induced (homolytic) cleavage of the pentazadiene bonds and formation of gaseous N2, which facilitates material failure at the irradiated spot.The recovery of optical transmission can be applied to optical memory, optical and micro-mechanical applications. The underlying mechanism of the phenomenon is discussed in terms of anelastic α- and β-relaxation (polymer backbone and chains/coils relaxation, respectively).