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Abstract Mixed crystals V1-xNbxO2 exist over the whole area of the quasibinary line VO2-NbO2. The existence of Nb5+ beside V3+ and V4+ on the V-rich side and V3+ beside Nb5+ and Nb4+ on the Nb-rich side of the mixed crystals is demonstrated by XANES-measurements. The compound VNbO4(V0.5Nb0.5O2) is described as a double oxide with vanadium only as V3+ and niobium only as Nb5+. At this point the electric...