Because of a very low thermodynamic stability, obtaining a pure monophasic compound of ferric pseudobrookite is quite difficult to achieve. Indeed, the low reticular energy of this phase leads easily to its decomposition and the occurrence of the secondary phases: hematite (Fe2O3) and/or rutile (TiO2). Samples with global composition Fe2-xTi1+xO5 (x = 0, 0.05, and 0.10) have been synthesized by the Pechini route and, thereafter, thermally treated at different temperatures. The concentrations of Fe2O3 and TiO2 secondary phases were accurately determined and correlated with the target compositions and the synthesis parameters, especially the thermal treatment temperature. As revealed by Mössbauer spectroscopy, all iron ions are at the III+ oxidation state. Thus, the formation of hematite or rutile as a secondary phase may be related to the occurrence of cationic vacancies within the pseudobrookite structure, with the amount of vacancies depending on the annealing temperature. In light of the presented results, it appears unreasonable to propose a "fixed" binary phase diagram for such a complex system. Furthermore, the occurrence of cationic vacancies induces a coloration change (darkening), preventing any industrial use of this reddish-brown pseudobrookite as a ceramic pigment.