The corrosion behavior of a Ni3A1–1 5at%Fe alloy has been studied in air and melted salts, and also that of Ni3Al alloys contained series boron in melted salts. The first alloy has two oxidation rate constants. Its initial oxidation activity energy is 319 kJ / mol. There was much FeAl2O4 formed at 950°C, which possessed better oxidation resistance than NiFe2O4, therefore the alloy had the best oxidation resistance at 950°C. It also had better sulfidation resistance than 00Cr19NillTi stainless steel at 850°C, but the alloy was sulfidized seriously at 950°C. The sulfides were FeS2 at 850°C and A12S3, Ni2S3 at 950°C. There were different initial oxides formed, which were Fe3O4 at 850°C, and mixture oxides of NiO, NiMoO4, A12O3 and NiAl2O4 at 950°C , respectively. The Ni3Al alloys with boron contents from 0 to 3.7at% had better sulfidation resistance than the stainless steel at 850°C, and the alloy with 1.37at%B was the best. The sulfides were the same in the boron containing Ni3Al alloys which were Al2S3 and Ni7S6.