The ZSM-5 zeolite (MFI structure, Si/Al = 40) was treated using NaOH and either oxalic acid or HCl to obtain hierarchical materials with different characteristics, followed by impregnation with vanadium oxides (V2O5) to generate redox-active sites. The impact of the multiple treatments on the efficiency and stability of the catalysts in the conversion of glycerol to acrolein and acrylic acid was investigated and correlated with catalyst porosity, acidity, and chemical composition. The treated and impregnated V2O5 catalysts were subjected to XRD, 27Al NMR, nitrogen physisorption, TPD-NH3, TG, and IJV Vis analyses, in order to associate the properties of the catalysts with their activities. The studies showed that the catalytic performance of the materials depended on the acidic and textural properties of the zeolites, which influenced both the dispersion of V2O5 and its interaction with the acid sites of the supporting zeolites. All the catalysts provided conversion values exceeding 65%, even after 6 h on glycerol stream. The distribution of products strongly reflected the effects of pore formation, acid treatment with oxalic acid or HCI, and the presence of vanadium oxide. The effects of these modifications resulted in higher selectivity to acrolein and acrylic acid, a reduced rate of coke accumulation in the zeolite, and a longer catalyst lifetime. (C) 2016 Elsevier B.V. All rights reserved.