Thermal degradation for glass fiber-reinforced polyamide 66 composite (PA 66) with respect of thermal exposure time has been investigated using optical microscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. As the thermal exposure time was prolonged, a slight increase in tensile strength for only initial stage and afterward, a proportional decrease of tensile strength was observed. These results can be explained by the increase of crystallinity, followed by the increase of crosslinking density, chain scission and the decrease in chain mobility, due to thermal oxidation with the exposure time. Fourier transform infrared spectroscopy results showed the increase of ketone peak and silica peak on the surface of thermally exposed PA 66. In addition, the thermal decomposition kinetics of PA 66 was analyzed using thermogravimetric analysis at three different heating rates. The relationship between activation energy and lifetime-prediction of PA 66 was investigated by several methodologies, such as statistical tool, UL 746B, Ozawa and Kissinger. The activation energy determined by thermogravimetric analysis had a relatively large value compared with that from the accelerated test. This may result in over-estimating the lifetime of PA 66. In this study, a master curve of exponential fitting has been developed to extrapolate the activation energy at various service temperatures.