The effect of different ions which are constituents of technical lignin sulfonates (LS) on chemo-enzymatic graft co-polymerization was determined. The application of the iron chelator desferrioxamine in the initial reaction mixture revealed that iron impurities of LS which catalyzed a Fenton-like reaction were crucial for the initiation of grafting, whereas calcium or chloride ions showed no such effect. The addition of laccase (ATCC 11235) to the reaction mixture which contained desferrioxamine caused a significantly higher yield compared to the control; this indicates a crucial effect of laccase with regard to the initiation of copolymerization. The involvement of laccase in the initiation of the graft copolymerization was additionally confirmed by the application of low molecular weight phenolics instead of LS. In the presence of the lignin-like substrates, 3,4-dihydroxybenzoic acid and guaiacol, the rate of the decomposition of t-butylhydroperoxide was significantly enhanced by laccase. It can be assumed that the enzymatically generated phenoxy radicals mediate the production of oxygen centered radicals (alkoxy or peroxy) which initiate grafting.