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The structure of V2TiO5 involves a distribution of the two metal species between two crystallographic sites. The sites between the shear planes are occupied solely by vanadium as VIII, while the shear-plane sites are occupied by both metal atom species, vanadium and titanium. An analysis of the metal-oxygen distances could not distinguish between the two reasonable alternatives for the valency distribution, viz VIII/TiIV or VIV/TiIII. By examining the XANES spectra of the title compound at both vanadium and titanium K edges the valency distribution can be confidently assigned as VIII/TiIV. The usefulness of XANES spectroscopy for solving similar problems involving valency ambiguity is evident.