Mesoporous silica-supported nano-crystalline sulfated zirconia catalysts were prepared via the sol-gel process using an in situ sulfation. The parameter studied in this work was the S/Zr molar ratio. The synthesized solids were characterized using XRD, N-2 physisorption, TG-DTA/SM, sulfur chemical analysis and adsorption-desorption of pyridine, and tested in the gas-phase acid-catalysed isomerization of n-hexane. The gelation process is highly affected by the sulfate loadings. Two gelation mechanisms were evidenced depending on the S/Zr molar ratio. The first one observed when 0.15 <= S/Zr <= 0.5, is characterized by a relatively high gelation rate. This mechanism favours the formation of two types of mesopores and a low percentage of retained sulfur. The second gelation mechanism occurs for higher S/Zr ratios: 0.5 <= S/Zr <= 1.2. In that case, slower gelation rates are observed. This slower gelation process leads to materials with reduced BET surface area but the amount of retained sulfur is increased. Appreciable catalytic properties were observed for the sample prepared with the highest S/Zr ratio, which presents the smallest size of sulfated zirconia crystallites and shows both Bronsted and Lewis acid sites on its surface. (c) 2007 Published by Elsevier B.V.