The operating efficiency and reliability of modern jet engines have undergone significant improvement largely owing to the advances of the materials science over the past 60 years. The use of both superalloys and TBCs in engine components such as turbine blades has made it possible for jet engines to operate at higher temperatures, allowing an optimal balance of fuel economy and thrust power.Despite the vast improvement in high temperature capability of superalloys, the utilization of TBCs has brought the concern of coating adhesion during their usage. TBCs are prone to spallation failure due to interfacial rumpling, which is driven primarily by thermal coefficient mismatch of the multi-layered structure. Although interfacial degradation of TBCs has been widely studied by detailed numerical and analytical models, the predicted results (i.e. stress state and rumpling amplitude) often deviate from that obtained by experiments. This is largely due to the lack of consideration of the influence of bond coat and substrate chemistry on the interfacial evolution of TBC systems. It is only in recent year that more and more study has been focused on studying the role of chemistry on the interfacial degradation of TBCs.The purpose of this PhD project is to clarify how the bond coat and substrate chemical compositions dictate the mechanisms of interfacial degradation, leading to the final spallation. A cross-sectional indentation technique was utilized to quantitatively characterize the adhesion of oxide-bond coat interface among 5 systematically prepared TBC systems. The adhesion of isothermally exposed oxide-bond coat interface was then correlated with different microstructure parameters, in an attempt to identify the key parameters controlling the TBC spallation lifetime. EBSD and EPMA analyses were conducted on the bond coat near the oxide-bond coat interface, in order to understand the relationship between the key parameters and specific alloying elements. The results clearly demonstrated that the phase transformation of bond coat near the oxide-bond coat interface plays the dominant role in the degradation of interfacial adhesion. Particularly, the co-existence of gamma prime and martensitic phases, each having very different thermomechanical response under thermal exposure, can generate a misfit stress in the TGO layer, and ultimately causes early TBC spallation. In addition, the phase transformation behavior has been closely associated with the inherent chemistry of the bond coat and substrate.