The corrosion resistance of several types of steel (AISI 410, 321, 316L, 904L) was determined in a liquid Bi-Li (5 mol.%) alloy (BLA) medium at 650 °C combining gravimetric analysis of steel samples and chemical analysis of corrosion products’ content accumulating in the BLA phase. Energy dispersive X-ray spectrometry, scanning electron microscopy, X-ray fluorescence and inductively coupled plasma–atomic emission spectrometry analysis were employed for characterizing steel structure and alloy composition. AISI 321, 316L and 904L nickel-containing corrosion-resistant steels underwent severe corrosion in BLA, and their corrosion rates depended on the nickel content in the material. AISI 410 steel exhibited the lowest corrosion rate of all the materials investigated, and this type of steel can be considered as a reasonable structural material for work in BLA environments. The corrosion rates of AISI 410, 321, 316L and 904L steels in BLA at 650 °C were 77, 244, 252 and 280 µm/year, respectively. It was also found that chromium was etched more intensively than iron from the surface of steel samples.