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Polyethylene imine hydrogel complexes with various salts of ferric and ferrous iron and also with complex salts of iron as well as insoluble ternary complexes of various composition: low cross-linked polyethylene imine hydrogel -copper (II) nitrate -sodium dodecylbenzylsulfate have been received. Their biocatalytic properties in the reaction of hydrogen peroxide decomposition (catalase activity) have been investigated. It was shown that catalase activity of complexes depends on the salts type and valence state of iron ions. The complexes of ferric iron as well as ternary complexes are most active in the reaction of hydrogen peroxide decomposition.