Polymers containing the Azo-benzene group have attracted attention due to anticipated uses such as materials for data storage, membranes with controllable permeability and materials with changeable solubility [1,2]. These expectations are due to the change in shape and dipole moment of the Azo-compound when excited by photo isomerization from the trans-state to the cis-state by UV light of ca 360 nm. Films of copolymers of poly-methyl methacrylate (PMMA) containing 8 wt-% Azo-benzene were photo isomerized with a UV lamp and then measured as a function of time in a lowenergy positron beam. The observed changes in the lifetime parameters as a function of time were in agreement with the thermal isomerization (decay) of the cis-isomer as measured by conventional UV spectroscopy. The results show that positron lifetime spectra at low energy are sensitive for the cis-trans isomerization of the Azo-compound, suggesting trapping and annihilation of positrons at free volume sites around the Azo-benzene groups.