The oxide ions of MoO₃ and V₂O₅ catalysts were exchanged with ¹⁸O tracer by a reduction-oxidation method and by a catalytic oxidation of but-1-ene or n-butane using ¹⁸O₂. The Raman band shifts of MoO₃ and V₂O₅ exchanged with ¹⁸O by the methods were examined. The two bands at 823 and 670 cm^-1 shifted to lower frequencies preferentially with MoO₃ while the band of terminal Mo=O oxygen at 998 cm^-1 was not shifted very much initially. With V₂O₅, the band at 700 cm^-1 shifted to lower frequencies more preferentially than the band of V=O oxygen at 998 cm^-1.  Applying the correlation between the Raman bands and the stretching modes in the literatures, the positions of oxide ions and the anion vacancies for redox reactions were estimated.