Molybdenum-based catalysts supported on Al2O3 doped with Ni, Cu, or Fe oxide were synthesized and used in ethylbenzene dehydrogenation to produce styrene. The molybdenum oxide was sup-ported using an unconventional route that combined the polymeric precursor method (Pechini) and wet impregnation on commercial alumina. The samples were characterized by X-ray diffraction (XRD), N2 adsorption-desorption isotherms, temperature-programmed reduction of H2 (H2-TPR), and thermogravimetric (TG) analysis. XRD results showed that the added metals were well dis-persed on the alumina support. The addition of the metal oxide (Ni, Cu, or Fe) of 2 wt% by wet im-pregnation did not affect the texture of the support. TPR results indicated a synergistic effect be-tween the dopant and molybdenum oxide. The catalytic tests showed ethylbenzene conversion of 28%–53% and styrene selectivity of 94%–97%, indicating that the addition of the dopant improved the catalytic performance, which was related to the redox mechanism. Molybdenum oxides play a fundamental role in the oxidative dehydrogenation of ethylbenzene to styrene by its redox and acid–base properties. The sample containing Cu showed an atypical result with increasing conver-sion during the reaction, which was due to metal reduction. The Ni-containing solid exhibited the highest amount of carbon deposited, shown by TG analysis after the catalytic test, which explained its lower catalytic stability and selectivity.