Plasma spraying of pure alumina in almost all of the normal spraying conditions results in metastable gamma phase only; in contrast titania-stabilized alumina on spraying results in stable alpha phase in considerable quantities along with metastable gamma phase. Formation of beta-Al2TiO5 and preferential evaporation of alumina leading to phase separated TiO2 have also been observed in as-sprayed alumina-titania samples. Preferential stabilization of the alpha phase in as-sprayed samples can be attributed to the Ti4+ cationic substitution and formation of charge compensating defects in the alpha-phased alumina lattice.