Using oxygen rather than air in coal-fired boilers has been studied for several years as a strategy to reduce NOx and concentrate CO2 for capture. In combination with flue gas recirculation higher levels of CO2 are expected but increased H2O and SO2 levels also may occur. In order to understand the role of substrate composition on corrosion a combination of commercial and model alloys are being investigated both with and without the presence of synthetic coal ash. The current work is focusing on 600°C with ferritic and austenitic steel coupons as well as Ni-base alloys and weld-overlay coupons for comparison. In simplified CO2-O2-H2O-Ar environments the combination of CO2 and H2O resulted in the highest oxidation rates with more than 20% Cr needed for protective behavior after 2000h compared to Ar-CO2 (3%Cr protective) and 100% H2O (>15%Cr protective).