We prepared high porous γ-Al2O3 samples via a modified sol-gel method in which polyvinyl-alcohol (PVA) was incorporated to hydrolysis water before the formation of boehmite sol with two different PVA contents (44 and 174 wt%). We compared our results with those of other γ-Al2O3 samples also prepared via sol-gel with different procedures; a sample without additives (sample S) and samples with the same contents of PVA but added to the already synthesized boehmite sol (A-samples); the latter as standard for evaluation of our modified sol-gel method (B-samples).Samples were characterized by means of XRD, adsorption-desorption isotherms of nitrogen at 77K and DTA-TG, and also were investigated against thermal cycling at 600 °C.Pore volume, porosity, BET area, and pore distribution were determined. B-sample with 44 wt% PVA showed similar characteristics to those of A-samples, while an important increase of pore volume, porosity and BET area (50%) was observed for sample with 174% PVA. Pore diameter of B-samples also exhibited a different behaviour with PVA content: addition of 44 wt% of PVA gave a 16% increase while 174 wt% PVA, 42%. These results indicated that adding PVA to the already sinthesized boehmite sol, mainly stabilizes the boehmite structure, without affecting it. On the contrary, incorporation of PVA before hydrolysis influences the particle size in the sol, greatly modifying the final boehmite network and giving place to larger pores in the final γ-Al2O3, this effect being significant when adding 174 wt% PVA.Results of thermal treatments at 600°C showed a decrease in BET area of all samples up to 80h, then stabilised. A minimal effect of the thermal treatments on the pore volume and porosity was observed in all samples while the pore diameter increased, this increase being most important in case of sample with 174 wt% PVA.