The free volume properties of a poly(methyl methacrylate)-azobenzene copolymer were for the first time directly probed by use of a low-energy positron lifetime beam with in-situ excitation capabilities, showing that the free volume cavity size was not appreciably influenced by photoisomerization and thermal isomerization in the temperature range 34-180 degreesC. lsomerization is therefore suggested to occur without any molecular rearrangement of the glassy polymer matrix, which would also account for the lack of any shift to shorter wavelengths for the photoisomerization occurring in a glassy polymer in comparison to a chloroform solution. A decrease in the thermal isomerization rate at room temperature caused by the glassy polymer is explained in terms of a model in which only a fraction of the azobenzene is free to isomerize. The cis-azobenzene was found to be an efficient inhibitor of positronium formation, which enabled measurements of thermal isomerization rates and changes in the steady-state concentration of cis-azobenzene for an illuminated sample as a function of temperature.