AbstractModel complexes of vanadate‐dependent peroxidases, viz. oxidovanadium(V) complexes of the general composition [VO(Hn–xL)], have been prepared and characterised. HnL is an n‐basic di‐ or trichiral aminodiethanol [HOCH(Ph)CH2]2NR, with R = N‐methylimidazolyl (H2LA), tris(hydroxymethyl)methyl (H5LB, 2 isomers), 2,3‐dihydroxypropyl (H4LC, 2 isomers) and 2‐hydroxy‐3‐trityloxypropyl (H3LD). These ligands form the complexes [VO(OH)(LA)], [VO(H2LB)], trigonal‐bipyramidal [VO(HLC)]tbp and octahedral Λ‐[VO(HLC)]oct. The ligands R,R,S‐H4LC and R,R,R‐H3LD, and the complexes Λ‐[VO(R,R,S‐HLC)]oct and [VO(R,R,S‐HLC)]tbp have been characterised by X‐ray structure analysis. The complexes [VO(H2LB)] and [VO(HLC)] were immobilised on Merrifield and Barlos resin by anchoring through a free alcoholic group in the ligand side‐chain R. {[VO(H2O)LE]}, an oxidovanadium(IV) complex tethered to Merrifield resin, was prepared by treating [VO(acac)2] with {HLE}, the immobilised Schiff base ligand obtained by condensation of salicylaldehyde with resin‐anchored lysine. The complexes and in situ systems ([VO(OiPr)3] + ligand) as well as the immobilised complexes were investigated for their catalytic activity in the oxygenation, by cumyl hydroperoxide, of thioanisol to its sulfoxide. All of the systems were active, with a selectivity (sulfoxide vs. sulfone) of 95–98 %. Satisfactory turnover rates and a chiral induction up to 37 % ee were observed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)