High Cr alloy 690 has replaced lower Cr alloy 600 in many critical pressurized water reactors components due to its superior resistance to intergranular stress corrosion cracking (IGSCC) in primary water environments. The increased Cr content (30 wt%) in alloy 690 is generally believed to promote formation of a protective chromia film on the surface that inhibits both corrosion and SCC. The current research investigates nanometer-scale corrosion/oxidation behavior at grain boundary and matrix regions. Stressed and unstressed specimens of cold-worked alloy 690 materials (shown to be susceptible to IGSCC in crack growth tests) have been exposed to simulated PWR water conditions at 360°C. Detailed surface and near-surface characterizations were then performed on cross-section samples starting with low kV backscatter scanning electron microscopy imaging to document the extent of localized corrosion and cracking. Selected surface and corrosion/crack tip regions are then prepared by focused ion beam milling for transmission electron microscopy and atom probe tomography analyses. A thin Cr-rich oxide film is detected across the entire surface but a continuous chromia film only forms above high-energy grain boundaries. No IG corrosion is observed however localized penetrative oxidation from surface is seen at distances >100 nm from the grain boundaries. Results will be discussed with respect to formation of precursor structures leading to SCC initiation.