Abstract The thermal cis to trans (Z to E) isomerization process following the photoisomerization of N,N- dimethylaminoazobenzene (methyl yellow) in a number of different solvent matrices; solutions, polymers and a liquid crystal are compared. In the solvents, dichloromethane, methanol, and polyacrylonitrile, a photoinduced stable cis isomer population could only be observed at −90[ddot]C. In other solvents such as toluene and polycarbonate, at room temperature, the half-life of the cis form was about thirty minutes. The trans to cis conversion of the methyl yellow was exploited in a low molar mass liquid crystal matrix. Photoinduced shifts of up to 17[ddot]C were observed in the nematic to isotropic phase transition temperature.