The microstructure and element distribution in the transition zone (TZ) of Alloy 52M buttering (52Mb) layer near the fusion boundary to the SA508III low alloy steel in a dissimilar metal weld joint with post-weld heat treatment (PWHT) is characterized. Two macroscopic TZs in the heat-affected zone have lower Cr and Ni contents than the bulk Alloy 52Mb. The first TZ near the fusion boundary has the lowest Cr and Ni compositions, accompanying the highest Fe content. Cr depletion and Ni enrichment along with slight Fe enrichment at the dendrite boundaries in the TZs, are more significant than those in the bulk Alloy 52Mb. The number and the maximum depth of local oxidation penetrations at the alloy-inner oxide interface based on the oxidation tests, the number and the maximum length of locally interdendritic cracks, as well as the average crack growth rate (CGR) in terms of the stress corrosion cracking (SCC) band based on the SCC tests in the first TZ are higher than those in the second TZ. The average SCC CGR is enhanced by macroscopic element dilution, while local oxidation penetration, as well as locally interdendritic SCC, are thought to be enhanced by both the macroscopic dilution of Cr in the TZs and the microscopic Cr depletion at dendrite boundaries.