This study introduces a novel method that utilizes evolved gas analysis with time-of-flight mass spectrometry (EGA-TOFMS) coupled with principal component analysis (PCA) and Kendrick mass defect (KMD) analysis, called EGA-PCA-KMD, to analyze complex structural changes in polymer materials during thermo-oxidative degradation. While EGA-TOFMS captures exact mass data related to the degradation components in the temperature-dependent mass spectra of the evolved products, numerous high-resolution mass spectra with large amounts of ion signals and varying intensities provide challenges for interpretation. To address this, we employed mathematical decomposition through PCA to selectively extract information about the ion series specific to the products that evolved from the degradation components. Additionally, KMD analysis was applied to the attribution of the exact mass signals extracted from the PCA, which categorizes and visualizes depending on the molecular compositions in a two-dimensional plot. The complex structural changes of the triblock copolymer thermoplastic elastomer and its nanocomposites containing nanodiamonds during thermo-oxidative degradation were elucidated using EGA-PCA-KMD to demonstrate the effectiveness of this characterization technique for polymer degradation. Furthermore, it is revealed that the formation of rigid matrix-filler interfacial interaction via the π-π stacking and chemical bonds in the nanocomposites contributes to improvement in the stability toward thermo-oxidative degradation. Our results highlight the benefits of EGA-PCA-KMD and provide valuable insights into polymer degradation.