A novel synthetic procedure for the functionalisation of styrenic cross-linked polymers with perfluorinated acyl chains has been reported. The effective significant grafting of the fluorinated moieties is supported by {1H}-13C and {19F}-13C NMR characterisations. This kind of polymer appears promising as catalytic support for a variety of reactions requiring a highly lipophilic catalyst. Indeed, the improved lipophilicity of the materials resulted in enhanced catalytic properties of the corresponding sulfonic materials in the reaction of esterification of a solution in a vegetable oil of stearic acid with methanol.