Enhancement of Brønsted acidity in silica-titania aerogel was achieved by loading both sulfate and vanadium onto the material. This phenomena could be due to formation of V(OSi)2OH-O-SO3 in the resulted sample. In contrast, no noticeable Brønsted acidity was detected in vanadium loaded silica-titania aerogel (V/ST). UV-vis DR analysis results showed that the amount of hydrated tetrahedral titanium species, which acts as oxidative site, increased significantly upon sulfation and vanadium loading on the surface of the aerogel. However, presence of vanadium in the samples tended to transform framework tetrahedral titanium to extra framework octahedral titanium structure. The catalytic performance of the samples were evaluated in consecutive transformation of 1-octene to 1,2-octanediol through formation of 1,2-epoxyoctane using aqueous H2O2.