Misch metal (Mm), consisting of Ce and La, was added to Ti–45Al–3Mo–2Nb alloys in order to investigate phase transformation and microstructural changes. The pseudo-binary phase diagram was estimated via PANDAT software™. The addition of Mm caused a decrease in both the fractions of α2/γ lamella and the β0 phase, and served as an important factor for a collapse of lamellar structures. In addition, Mm significantly decreased the colony size of the alloy, resulting in an increase in high-temperature tensile yield strength of ~ 40% for the alloys with 0.3 at% Mm at 800 °C. It appears that the addition of Mm affects the phase stability and increase the proportion of the γ phase. The microstructural changes, with respect to Mm additions, were discussed in terms of structural observations during isothermal heat treatments.