The feasibility of increasing the deportment of titanium species and the stability of the pseudobrookite solid solution (M3O5) in a titaniferous slag was investigated, to facilitate the valourisation of titaniferous slags. Thermochemical simulations using FactSage™ software, ver 8.3 (by Thermofact/CRTC and GTT-Technologies), and equilibration-quench experiments were conducted using an appropriate synthetic titaniferous slag composition in an oxygen partial pressure (pO2) ranging from air to 10-16 atm under non-isothermal conditions. The temperature-pressure phase stability diagram for the synthetic slag containing 37.19 per cent TiO2, 19.69 per cent SiO2, 13.12 per cent Al2O3, 16.00 per cent CaO and 14.00 per cent MgO showed that the spinel solid solution (M3O4) was the primary phase until a pO2 of 10-10.5 atm, thereafter M3O5 was the primary phase until a pO2 10-13.2 atm. M3O4 again was the primary phase between a pO2 10-13.2 and 10-16 atm. The changeover of the primary phase coincided with an increase in the liquidus surface. When cooling the slag in a pO2 of 10-16 atm, M3O5 crystallised as a ternary phase that showed a rapid increase in mass while that of the primary M3O4 phase decreased and that of the secondary perovskite (CaTiO3) phase increased at a slower rate. At 1300°C under sub-liquidus conditions, the contents of M3O5, M3O4 and CaTiO3 were about 20 per cent, 15 per cent, and 11 per cent, respectively. Experimental results showed that the Ti3+/Ti4+ mass ratio in the M3O5 phase, ie a measure of the reduction of titanium species, is not considerably sensitive to equilibration temperature in the reviewed range. Slow cooling and minimum/no oxidation during cooling of titaniferous slag would increase the deportment of titanium species to, and the growth and stability of the M3O5 phase.