Mill scale (MS) has a potential to use as an iron source because of its high iron content. MS mainly consists of a mixture of iron oxides, metallic iron and other base metal oxides. MS is formed on the surfaces of steel ingots during continuous casting as a waste material. In this study, the use of MS as an iron source for the production of carbon-free iron containing alloys (unalloyed iron, Fe-Ni, Fe-Cr-Ni, Fe-Cr-Ni-Mo) via a metallothermic reduction process was investigated. Thermodynamic calculations and the experimental studies were performed on the basis of 100 g of MS. The effects of different stoichiometric amounts of MS and aluminum (Al) powders (as reductant) were investigated for the production of unalloyed Fe. While, different amount of metal oxide ratios and their effects on metal recoveries, compositions and microstructure of final alloys were studied during Fe-based alloys production. The highest iron recovery during unalloyed Fe production was obtained as 95.14% by using 100 g of MS and 100% stoichiometric Al (28.6 g) containing mixture. In Fe-based alloys production series, the highest metal recovery values were reached up to 95.0% for Fe, 95.1% for Ni, 68.3% for Cr and 77.2% for Mo, respectively.