An alternative way of producing alumina, called the Pedersen process, is suggested in the current study. It is a pyro- and hydrometallurgical process, the main advantage being the valorization of the bauxite residue. In the present research, the smelting reduction of bauxite residue and a CaCO3-rich bauxite beneficiation by-product is studied to produce a calcium-aluminate slag and pig iron. Based on the results, increasing the CaO/Al2O3 ratio in the produced slags, can lead to the formation of phases that are considered leachable for alumina recovery, as 12CaO.7Al2O3, CaO.Al2O3, 3CaO.Al2O3. An optimum wt%CaO/wt%Al2O3 ratio of 1.5 is defined for the formation of a slag with more leachable phases. Proper slag and metal separation occurred, indicating the feasibility of producing two valuable byproducts applying the Pedersen process.