Flow-accelerated corrosion (FAC) preferentially attacks the downstream heat-affected zone of the root-pass weld in steam pipe systems. A detailed characterization identifies the fusion boundary as the initiation location for the attack. Alloying elements are found depleted along the weld fusion boundary, and multiple welding thermal cycles and repetitive austenite-to-ferrite phase transformations result in an increased proportion of grains with Goss {110} texture along the fusion boundary. The synergistic effects of chemical segregation and the Schmid factor may contribute to the preferential initiation of FAC cracks along the root weld fusion boundary, making it the weakest link for FAC attack in steam pipe girth welds.