This presentation will provide new insights and ideas to address the relationship among environmental exposure parameters, the presence of applied and residual stress, and microstructure/metallurgy performance. Electrochemical screening and sensing techniques have been explored to assess local corrosion reactions, selective dissolution and passivation behavior, and to observe the nucleation of environmentally assisted cracking (EAC). Typical examples and innovative approaches to advance our mechanistic understanding of localized corrosion and EAC are discussed, with the aim of better understanding mechanistic behavior and extending component lifetime. Techniques for measuring corrosion kinetic behavior, passive film composition, and crack-nucleation propensity are introduced, and the application of electrochemical techniques is elaborated. A range of new ideas is presented, including the application of electrochemically controlled micro-/nano-indentation tests, in situ confocal microscopy of hydrogen embrittlement (HE), and 2D/3D/4D corrosion and crack growth measurements using advanced imaging methods. These tests are then combined with chemical fingerprinting of corrosion products using (spectral) imaging approaches. The development of corrosion chemistry is observed over time, yielding information about local passivation behavior under redox conditions. We present work on aluminum alloys, stainless steels, and Ni-base alloys, addressing material behavior for marine exposure, petrochemical applications, and nuclear/radwaste exposure regimes. Results from different characterization techniques will be compared and correlated to their electrochemical responses.