Well-controlled fine MgTi2O5 powders, with pseudobrookite-type structure, are desired toward various industrial applications, however, commercial powders are hardly available to date. In this study, we focused the processing and characterization of well-controlled MgTi2O5 powders with/without LiF additive. MgCO3 (basic) and TiO2 anatase powders with/without 0.5 wt. % LiF additive were calcined in air at 1100 °C for 2 h to obtain the MgTi2O5 powders. SEM observation revealed that the non-doped MgTi2O5 powder consisted of equiaxed particles with the diameter of 0.5-1.5 μm, whereas, the LiF-doped MgTi2O5 powder consisted of elongated particles with the length of ~ 5-10 μm and the diameter of ~1.0-1.5 μm. The smooth surface of elongated MgTi2O5 particles demonstrates the effect of LiF doping as a flux, i.e., liquid phase formation during the reaction.