VOX-SiO2 catalysts have been synthesized by the one-pot method using different vanadium precursors, namely, ammonium meta-vanadate (NH4VO3; VO3-, V5+), vanadium acetylacetonate [V(acac)(3); organic complex, V3+], and vanadyl sulfate (VOSO4; VO2+, V4+). The influence of different vanadium precursors on the structure-performance relationship of these catalysts is studied on the propane dehydrogenation (PDH) reaction. The catalysts derived from VO3- attain a mesoporous structure with fairly high specific surface area and large pore volume, while those prepared with V(acac)(3) or VOSO4 display a microporous structure. It is noted that VOX-SiO2 catalysts derived from NH4VO3 present a better catalytic performance, and low-polymerized VOX species display better intrinsic activity compared with isolated species. This study may contribute to the selection of vanadium precursors for the one-pot synthesis.