The vanadium-doped mesoporous silica nanospheres ( n V−MSNs) with worm−like porous structure were successfully synthesized by simple sol−gel method and applied to propane dehydrogenation (PDH) reaction. The moderate introduction of vanadium species didn't affect the self−assembly of the worm−like porous structure of support. The prepared samples were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectra (XPS), temperature–programmed desorption (TPD) of NH 3 and temperature-programmed reduction (TPR) with H 2 to investigate the influence of the chemical states of VO X on the catalytic properties in PDH reaction. It is found that the appropriate amount and high dispersion degree of VO X species of the n V−MSNs catalyst is the key to obtain excellent catalytic performance in PDH. It is shown that 9V−MSNs catalyst exhibits optimum reaction activity with an initial propane conversion of 50.6% at 600 ° C. The catalyst obtains the maximum percentage of active V V species, and has better vanadium dispersion than others, which is demonstrated by Raman and XPS analysis. 9V−MSNs catalyst also exhibits outstanding activity and stability in reaction−regeneration for six cycles. Hence, the prepared n V−MSNs catalysts hold immense potential to further development in application of PDH. • Vanadium-doped mesoporous silica nanospheres ( n V-MSNs) were synthesized. • n V-MSNs show superior TOF value for propane dehydrogenation reaction. • Vanadium content influences its chemical states and polymerization degree. • The deactivated catalyst can be fully recovered after regeneration.