Using two techniques of thermogravimetry and differential scanning calorimetry under O2 gas atmosphere from 25 to 600°C, the thermal behavior of laboratory-produced compound lead(IV) oxide α-PbO2 was investigated. The identity of products at different stages were confirmed by XRD technique. Both techniques produced similar results supporting the same decomposition stages for the compound. Three distinct energy changes were observed, namely, two endothermic and one exothermic in DSC. The amount of ΔH for each peak is also reported.