The polarographic behavior of 3-methyl-4-(2’-substituted benzeneazo)-2-isoxazolin-5-ones has been studied in 50% v/v dimethylformamide solution in Britton-Robinson buffer of pH 4.1 at different temperatures (303.15-333.15 K). The reduction is diffusion-controlled and becomes irreversible at higher temperatures. The shift of E1/2 values toward more negative potentials and a decrease in the values alphan(a) and k(f,h)o suggests that the electrode reaction becomes more irreversible at elevated temperatures. Thermodynamic parameters were evaluated at the different temperatures studied. The results can be explained in the light of a correlation between electrode kinetics and double-layer structure.