Epoxidation of allylic alcohols and cyclohexene with TBHP and titania-silica aerogels containing 1 and 5 wt% TiO2 has been studied. For the oxidation of geraniol and cyclohexenol, the regio- and diastereoselectivities and kinetic data indicate an OH-assisted mechanism involving a dative bond between the OH group and the Ti site. This mechanism is disabled in the oxidation of cyclooctenol due to steric hindrance. The moderate regio- and diastereoselectivities of the aerogels, compared with those of TS-1 and the homogeneous model Ti(OSiMe3)(4), are attributed to the presence of non-isolated Ti sites and to a "silanol-assisted'' mechanism, according to which model the allylic alcohol is anchored to a neighboring SiOH group instead of the Ti-peroxo complex. Kinetic analysis of the initial transient period revealed rapid catalyst restructuring during the first few turnovers. A feasible explanation is the breaking of Si-O-Ti linkages of the carefully predried aerogels by water or TBHP, resulting in active Ti sites with remarkably different catalytic properties.