Recent materials development for solid oxide fuel cells (SOFCs) has been driven by the recognition of simultaneous improvement over the activity (e.g., system performance) and durability (e.g., stability of the performance). Structure and bonding of SOFC components and devices lie at the heart of the viable approaches to achieve these improvements. We will start this paper with a brief illustration of structure and bonding in SOFCs, followed by detailed analysis on the role of local structure and chemical bonding on the electrochemical performance and performance stability of SOFCs.