The ability of the litter-decomposing basidiomycete Stropharia rugosoannulata DSM 11372 to degrade a wide range of structurally different environmental pollutants such as polycyclic aromatic hydrocarbons (PAHs: phenanthrene, anthracene, fluorene, pyrene, and fluoranthene), synthetic anthraquinone dyes containing condensed aromatic rings, environmentally relevant alkylphenol and oxyethylated alkylphenol representatives, and oil was demonstrated within the present study. 9,10-Anthraquinone, phenanthrene-9,10-quinone, and 9-fluorenone were identified as products of anthracene, phenanthrene, and fluorene degradation, respectively. Fungal degradation was accompanied by the production of the ligninolytic enzymes: laccase and Mn peroxidase, suggesting their involvement in pollutant degradation. Extracellular polysaccharide(s) (EPS) and emulsifying compound(s) were concomitantly produced. EPS composed of mannose, glucose, and galactose was isolated from the cultivation medium, and its effects on catalytic properties of purified laccase from S. rugosoannulata (the dominating ligninolytic enzyme under the applied conditions) were studied. A simultaneous decrease of K and V values observed for the enzymatic oxidation of non-phenolic (2,2-azino-bis-(3-ethylbenzthiazoline-6-sulphonic acid) diammonium salt; ABTS) and phenolic compounds (2,6-dimethoxyphenol) in presence of EPS suggest an interaction of EPS and laccase resulting in a modulation of the catalytic performance of the enzyme, which has, to the best of our knowledge, not been reported before. In line with such a modulation, the laccase-catalyzed oxidation of natural aromatic compounds (veratryl alcohol, adlerol) and environmental pollutants (the alkylphenol representative nonylphenol, the diphenylmethane derivative bisphenol A, and the PAH representative anthracene) was found to be enhanced in presence of EPS. The relevance of such effects for real environmental processes and their implications remain to be investigated.