TiAl, TA6V and titanium coupons were treated by a phosphoric acid solution by dipping. They were then submitted to a heat treatment and, in the case of TiAl and TA6V, to high temperature discontinuous oxidation under laboratory air. The H3PO4 treatment allowed to decrease the mass gains for TiAl and TA6V, in particular during the first 100 hours. XRD analyses demonstrated for the three substrates the formation of a pyrophosphate layer during the heating period. This pyrophosphate evolved towards TiO2 with oxidation time increase, quicker for smaller aluminium content (or higher titanium content) in the metallic substrate. The decrease of mass gains was attributed to a diffusion barrier effect of the pyrophosphate layer as long as it was present.