SYNOPSISHorseradish peroxidase catalyzes the copolymerization of phenols with kraft lignin in aqueous-organic solvent mixtures. Nearly all of the lignin and over one-third of the phenol (either p-cresol or p-phenylphenol) is incorporated into the copolymer which is highly insoluble in dimethylformamide (DMF) , presumably because of crosslinking of lignin molecules via polyphenol bridges. The copolymer consists of 80% lignin, by weight. In the absence of a phenol, lignin is polymerized into a noncrosslinked, DMF-soluble material. Thermal analysis shows that the copolymerization of phenols with lignin results in a material with markedly lower glass transition temperatures and higher (and more uniform) curing exotherms. The materials appear to act as thermosets and may have application as replacements of conventional phenolic resins. 0 1993 John Wiley & Sons, Inc.