Isolated VOx-species supported on MCM-41 prepared with V(t-BuO)(3)O were characterized by ICP-AES, BET, Raman, XRD, and SEM analyses. Isobutane dehydrogenation reactions were carried out under oxygen lean, oxygen-free, and oxygen-rich conditions to evaluate these synthesized catalysts. The results showed that the catalysts prepared with V(t-BuO)(3)O exhibited a VOx dispersion that was higher than those prepared by impregnation with NH4VO3. Under oxygen-lean conditions, COx and coke formation were significantly suppressed. An isobutene yield above 40% and isobutene selectivity above 85% were achieved over MCM-41-supported isolated VOx species during at least 40 h on-stream combined oxidative and non-oxidative isobutane dehydrogenation.