The Schiff base (H₂fsal-ohyba) derived from 3-formylsalicylic acid and o-hydroxybenzylamine has been covalently bonded to chloromethylated polystyrene cross-linked with 5% divinylbenzene (abbreviated as PS-H₂fsal-ohyba, I). Treatment of [VO(acac)₂] with PS-H₂fsal-ohyba in dimethylformamide (DMF) gave the oxovanadium(IV) complex PS-[VO(fsal-ohyba)·DMF] (1). Complex 1 can be oxidized into the dioxovanadium(V) species, PS-K[VO₂(fsal-ohyba)] (2) on aerial oxidation in the presence of KOH or into the oxoperoxo species, PS-K[VO(O₂)(fsal-ohyba)] (3) in the presence of H₂O₂ and KOH in DMF suspension. Similarly, PS-[MoO₂(fsal-ohyba)·DMF] (4) has been isolated by the reaction of [MoO₂(acac)₂] with PS-H₂fsal-ohyba. All these complexes have been characterised by various techniques. These complexes catalyse the oxidation of styrene, ethylbenzene and phenol efficiently. Styrene gives five reaction products namely styrene oxide, benzaldehyde, 1-phenylethane-1,2-diol, benzoic acid and phenylacetaldehyde, while ethylbenzene gives benzaldehyde, phenyl acetic acid, styrene and 1-phenylethane-1,2-diol. The oxidation products of phenol are catechol and p-hydroquinone. These catalysts are also able to catalyse the oxidative bromination of salicylaldehyde to 5-bromosalicylaldehyde with ca. 80% selectively in the presence of aqueous 30% H₂O₂/KBr, a reaction similar to that exhibited by vanadate-dependent haloperoxidases. Their corresponding neat complexes have also been prepared and their catalytic activities have been compared.