In this study, FeCr coatings with different percentages of chromium were deposited on Grade 91 steel substrates by HVOF spraying, followed by aluminum enrichment via pack cementation. Overaluminizing parameters were optimized to prevent changes in the substrate microstructure, making it possible to determine the role of Cr and the effect of Al enrichment on anticorrosion behavior. The combination of HVOF spraying and pack cementation are shown to be adequate techniques for depositing intermediate and top layers in protective coating systems.