Epoxidation of alkenes with hydrogen peroxide was performed with polystyrene-supported peroxotungstic catalytic species. These peroxo species were complexed by several phosphorus(V) ligands such as phosphine oxides, phosphonic acids and their related amides grafted onto the polymeric matrices through sequential reactions. The efficiencies and the possibilities of repeated uses of these catalysts are related to the kind of the macroligand and its polymeric backbone.