The durability of PEM fuel cell materials is essential to application longevity. This research explores the limits of thermal stability of platinum/Vulcan XC 72 catalysts and a 46 wt % Pt/Vulcan XC 72/Nafion catalyst layer. The thermal stability of Pt/V ulcan XC 72 catalysts and the PEM fuel cell catalyst layer is studied by thermal gravimetric analysis (TGA) in air. The products of decomposition are analyzed with TGA coupled with mass spectrometry (TGA-MS). Low temperature (100-200 degrees C) carbon combustion in the presence of platinum is confirmed. The high precision and sensitivity of TGA allows differentiation of two oxidative/mass loss regimes for 46% Pt/C. The presence of surface protective groups raises the activation energy for the low-temperature/low-conversion (<= 5%) oxidation of 46% Pt/Vulcan XC 72 (197 13 kJ/mol) compared to a higher temperature/higher conversion level (10-30%) process (140 10 kJ/mol). In PEM fuel cell catalyst layers, the thermal decomposition temperature of Nafion is lowered by about 100 degrees C to 300 degrees C in the presence of Pt/C catalysts. As a result of the above studies it was found that TGA is convenient for the determination of Pt wt % in catalyst-coated membranes.