The V2O5/SiO2 catalysts promoted by fluoride anion and prepared with different F adding sequences were investigated. The samples were characterized by X-ray photoelectron spectroscopy (XPS), N2 adsorption–desorption, scanning electron microscopy (SEM), X-ray powder diffraction (XRD), temperature-programmed reduction (TPR), oxygen temperature-programmed desorption (O2-TPD) techniques and oxidative dehydrogenation reaction measurements. The results indicated that the fluoride impregnation sequence had a significant effect on the structure and selectivity of propene. Co-impregnation prepared VOF–C catalyst showed a better performance in the ODP reaction. The C3H6 selectivity was 74.9% at 480 °C, compared to 60.9% of V–Si–O sample without promotion. The propane conversion and propene yield were also better. The fluoride addition enhanced the mobility of oxygen in the catalyst.