Hydrophobic amorphous mixed oxides AM-(Ti3Si40Si)-Si-Me were prepared in the absence of modifiers as true xerogels with a narrow mesopore distribution around 3 nm. These materials selectively catalyze the quantitative conversion of olefins and allyl alcohols with an excess of oxidizing agent (TBHP). Regio-and chemoselectivity are comparable to literature data, most commonly obtained with hydrophilic aerogel catalysts and large excesses of olefin.