Basic bricks with Cr2O3 from chrome ore, as the spinel forming oxide, are used in the non-ferrous industry because of their corrosion resistance against fayalite-type slags, rich in FeO. Our objective in this study was to replace Cr3+ with Me4+ ions, which along with Fe3+ could maintain the spinel formation capability with MgO and perform similarly against fayalite slags in non-ferrous furnaces. Our preliminary research studies showed that Cr-free spinels in the MgO-Al2O3-FeOx-Me4+O2 systems could perform against fayalite slags similar to the complex (Mg2+, Fe2+)O·(Cr3+, Fe3+, Al3+)2O3 spinel, the main corrosion resistant component in the magnesia-chrome bricks. The incorporation of iron oxide in the MgO-Al2O3-Me4+O2 systems would contribute to reactive sintering and also in decreasing the solubility of both the ferrous and ferric ions present in the fayalite slag. Phase analysis on stoichiometric mixes showed that the use of tetravalent cation oxides like tin dioxide (SnO2) and titanium dioxide (TiO2) can induce high solubility of spinel in magnesia. In order to maintain charge balance, two trivalent cations were replaced by a tetravalent and a bivalent cation causing the additional bivalent cation to occupy the octahedral position thereby creating an inversion in position of the bivalent ions similar to the behaviour exhibited by Fe3+ occupying tetrahedral site in complex spinel phase of magnesia-chrome ceramics. Most of the magnesia-chrome refractories have ~60 wt. % MgO and hence our experimental mixes contained that amount and called “magnesia-rich” compositions, to be distinguished from the stoichiometric MgAl2O4 spinel. Our findings showed that the incorporation of nano TiO2 powders reduces the temperature of spinel formation as the diffusion path is shortened and thus activates both synthesis and sintering. Compositions containing 60 wt. % magnesia with alumina, nano TiO2 and Fe2O3 fired below 1500°C for 3 hours resulted in complete spinel formation and open porosity less than 5%.