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This paper describes the immobilization of the commercial synthetic tetrakis(pentafluorophenyl) porphine-iron(III) chloride on pyridyl-functionalized crosslinked poly(vinyl alcohol) and the catalytic activity of the adduct towards oxidation of selected organic substrates by hydrogen peroxide. The obtained adduct was characterized by UV/vis and IR spectroscopies. It showed a noticeable lignin-peroxidase-like catalytic activity; moreover a dramatic activity enhancement was observed in the presence of Mn²⁺ under certain experimental conditions, so the preparation could well be classified as a manganese-peroxidase-like catalyst leading to a transient Mn(III) species. Conversion yields for some aromatic compounds (bio)chemically related to lignin, kinetics and operational features of the adduct are also reported.