A differential scanning calorimetry study of the thermal behavior of nevirapine and azidothymidine in water solution was carried out. For nevirapine scan rate dependent and irreversible endothermic peak were found. Thermal degradation of nevirapine as well as NVP – AZT mixture is relatively well described by the model involving only one irreversible step determined by a first-order rate constant. The estimated kinetic constants and activation energies indicate that the degradation process proceeds slower for nevirapine in presence of AZT ligands than without them.