Abstract: Fe–S compounds with hexagonal crystal structure are potential hydrogen permeation barrier during H₂S corrosion. Hexagonal system Fe–S films were prepared on carbon steel through corrosion and CVD deposition, and the barrier effect of different Fe–S films on hydrogen permeation was tested using electrochemical hydrogen permeation method. After that, the electrical properties of Fe–S compound during phase transformation were measured using thermoelectric measurement system. Results show that the mackinawite has no obvious barrier effect on hydrogen penetration, as a p-type semiconductor, and pyrrhotite (including troilite) has obvious barrier effect on hydrogen penetration, as an n-type semiconductor. Hydrogen permeation tests showed peak permeation performance when the surface was deposited with a continuous film of pyrrhotite (Fe_1–xS) and troilite. The FeS compounds suppressed hydrogen permeation by the promotion of the hydrogen evolution reaction, semiconducting inversion from p- to n-type, and the migration of ions at the interface.