Ti-peroxide pillared layered double hydroxides (LDHs) have been prepared for the first time using water-soluble Ti-peroxide as an intercalating precursor. It is novel and alluring that the whole preparation procedure does not involve any usage of organic or chlorine-containing hazards. Intercalated into the LDH interlayer region, Ti-peroxide is prevented partially from condensation in the solvent evaporation. The interlayer Ti-O-2 unit exists in triangular (eta(2)) structure with C-2v symmetry in most cases, giving an interlayer gallery of 0.50-0.60 nm. But in the case of pH 4.0, monodentate (eta(1)) structure is also observed, giving an interlayer gallery of 0.70 nm. All the Ti-peroxide pillared LDHs prepared in this work show catalytic activity in the selective oxidation of thioether. The Ti-peroxide introduced into the interlayer regions of Mg/Al LDH with a particle size of around 50-120 rim exhibits better recyclability than Ti-peroxide gel, either in bulk or adsorbed on the exterior surface of LDH particles. (C) 2009 American Institute of Chemical Engineers AIChE J, 56: 1352-1362, 2010