The thermal degradation, under oxidative pyrolysis conditions, of two synthetic lubricating base oils, poly-α-olefin (PAO) and di-ester (DE), was investigated. The main objective of the study was to characterize their behavior in simulated “areo-engine” conditions, i.e. compared the thermal stability and identified the products of thermal decomposition as a function of exposure temperature. Detailed characterizations of products were performed with Fourier transform infrared spectrometry (FTIR), gas chromatography/ mass spectrometry (GC/MS), viscosity experiments and four-ball tests. The results showed that PAO had the lower thermal stability, being degraded at 200°C different from 300°C for DE. The degradation also effected the tribological properties of lubricating oil. Several by-products were identified during the thermal degradation of two lubricants. The majority of PAO products consisted of alkanes and olefins, while more oxygen-containing organic compounds were detected in DE samples according to the observation of GC/MS analysis. The related reaction mechanisms were discussed according to the experimental results.