Titanosilicate zeolite beads with hierarchical porosity and 0.2-0.5 mm diameter (HPB-TS-1) have been synthesized from a titanosilicate solution, employing a porous anion-exchange resin as shape- and structure-directing template. The characterization results showed the existence of crystalline TS-1 nanoparticles and of a network of connected large meso/macropores in the interior of the beads. These bead materials are active and selective heterogeneous catalysts for two classes of industrially relevant oxidation reactions: the hydroxylation of phenol and the epoxidation of alkenes. In both cases, a green oxidant such as hydrogen peroxide was utilized. HPB-TS-1 beads displayed high activity in the hydroxylation of phenol, due to their crystalline TS-1 structure with isolated tetrahedral Ti species. In the epoxidation of cyclohexene, HPB-TS-1 gave conversion comparable to that over a benchmark catalyst such as Ti-MCM-41, but more than double yield and selectivity of the target product, cyclohexene oxide. HPB-TS-1 was also active and selective in the epoxidation of other bulky alkenes, i.e., cis-cyclooctene and trans, trans, cis-1,5,9-cyclododecatriene. The catalytic performance of HPB-TS-1 stems from the presence of crystalline TS-1 nanodomains, which are accessible through a network of mesoimacropores within the beads. Notably, the bead format of these catalysts causes their spontaneous settling upon cessation of the agitation, thus enabling their straightforward separation from the reaction mixture. The HPB-TS-1 catalysts could be efficiently recycled in the hydroxylation of phenol with aqueous H2O2 via a calcination approach. (C) 2015 Elsevier Inc. All rights reserved.