Effect of zirconium presence in the silica framework and content and speciation of vanadium surface oxocomplexes on the catalytic behavior of VOx/Zr–SBA-15 catalysts in oxidative dehydrogenation of ethanol was investigated. Experimental results bring evidence of successful incorporation of zirconium into ordered mesoporous silica framework with the preservation of ordered mesoporosity by hydrothermal template base synthesis method. The presence of zirconium in the SBA-15 framework increases reducibility of vanadium species and acidity of the catalysts. Catalytic data also reveal that oligomeric/polymeric tetrahedrally coordinated vanadium species exhibit higher activity in ethanol oxidative dehydrogenation than monomeric complexes. In addition, comparison of the catalytic performance of VOx/Zr–SBA-15 catalysts with VOx/SBA-15 catalysts showed that catalytic properties of VOx/Zr–SBA-15 catalysts can be tuned by incorporation of controlled amount of zirconium into silica framework.