Vanadium crystalline glasses were prepared and investigated through surface area measurement, X-ray diffraction, chemical analysis and catalytic oxidation as a probe reaction. The vanadium based glasses were prepared by fusing V₂O₅, P₂O₅ and B₂O₃ mixtures with different compositions and annealling conditions. The prepared glasses were leached in acidic solution, dried and calcined sequentially. From the results of surface area analysis and chemical analysis of V⁴⁺/V⁵⁺ ratio, it was found that the glasses were porous mate-rials of which surface area is about 1m²/g in binary system and 5-10m²/g in ternary system. The V⁴⁺/V⁵⁺ ratio increased with P₂O₅ ratio for V₂O₅-P₂O₅ ginary glass. X-ray diffraction analysis showed that the fresh glass was amorphous but it changed to crystalline as it was annealled. Through the catalytic oxidation of methylcyclopentane, cyclopentane and cyclopentadiene, catalytic activity and selectivity of maleic-anhydride on vanadium based glasses were studied. As to geometric and chemical defference between V₂O₅-P₂O₅ and V₂O₅-P₂O₅-B₂O₅-B₂O₃ systems, the reaction showed also different results. Binary catalysts had less than 10% yield of maleic anhydride, but ternary catalysts had maximum 50% yield of maleic anhydride for cyclopentadiene.