Corrosion-resistant Ni3(Si,Nb) alloys are promising materials of construction for hydrogen-production systems based on the sulfur-iodine thermochemical cycle. In this work, the corrosion rates of three differentNi3(Si,Nb) alloys were measured in boiling 70 wt.% sulfuric acid and a three-stage corrosion mechanism was identified, based on the composition and morphology of surface scale that developed. The α(Ni) +β(Ni3Si) eutectic constituent of the alloy microstructure was selectively attacked by acid and, when present, is detrimental to corrosion resistance. The G-phase (Ni16Si17Nb6) is more passive than the β-matrix and seems to contribute to a lower steady-state corrosion rate.