The kinetics of the recombinant Coprinus cinereus peroxidase-catalyzed 2-naphthol oxidation was investigated in the presence of rhamnolipid biosurfactant JBR425 and synthetic surfactant Surfynol465 at pH 5.5 and 250C, with concentrations of (bio)surfactants both less than critical micelle concentrations (CMC) and larger than CMC. It was shown that monomers of JBR425 as well as monomers of Surfynol465 had an enhancing effect on the conversion of 2-naphthol in dose response manner and did not influence the initial rate of 2-naphthol oxidation. The results were accounted by a scheme, which contains a stadium of enzyme inhibition by oligomeric 2-naphthol oxidation products. The action of the biosurfactant's (or synthetic surfactant's) monomers was explained by avoidance of the enzyme active center clothing with oligomers. Similar results have demonstrated the potential of rhamnolipid biosurfactant JBR425 due to its biodegradability. When biosurfactants' concentrations are larger than CMC, (bio)surfactants have an opposite effect on the oxidation of 2-naphthol by peroxidase.