The olefins product are more reactive than the corresponding alkanes, and may easily be super-oxidised into CO and CO2 in selective oxidation of alkanes. The proper balance of acid and base sites on the V-based catalyst surface plays a decisive role in limiting the complete oxidation of alkanes. Therefore, our goal was to evaluate the promoting effect of alkali metals and the support effect using boehmite as precursor for the propane oxidative dehydrogenation (ODH) reaction. Catalysts were prepared via co-impregnation of V and Na or K on a synthesized alumina support. The following characterization techniques were used: N2 adsorption-desorption, X-ray diffraction (XRD), temperature programmed reduction (TPR) and isopropanol decomposition testes to evaluate the acid-base character. The catalyst performance in the propane ODH reaction was evaluated at the O2:C3H8:He molar ratios of 5:2:4, 6:1:4, and 4:3:4. The K-doped catalysts exhibited higher propene selectivity owing to the modification of acid-base character that rendered the weaker interaction between olefinic intermediate and more basic catalyst surface. A high molar fraction of O2 of the reaction mixture minimized coke formation and a high reoxidation rate possibly increased catalytic activity and propene selectivity.