Pb-Caustic Stress Corrosion Cracking initiation was studied on Alloy 690TT at 315°C. Advanced electron microscopy techniques revealed that cracking mainly initiated intergranularly following the oxidation of Cr-rich grain boundary carbides. This finding explains the higher resistance to crack nucleation of the as-received surfaces compared to polished ones, because the grain boundaries of the ultrafine-grained near-surface layer were not decorated with carbides. It is also proposed that dislocation entanglements, typical of a cold-worked surface, attenuated the emission of dislocations at the surface. Once initiated, cracking continued due to Pb incorporation in the oxide, which weakened the passive layer and enhanced slip dissolution.