Toluene is a compound that often occurs in municipal wastewater ranging from detectable levels up to 237 μg/L. Before the year 2000, the presence of the aromatic hydrocarbons was assigned only to external sources. The Enhanced Biological Nutrients Removal Processes (EBNRP) work according to many different schemes and technologies. For high-efficiency biological denitrification and dephosphatation processes, the presence of volatile fatty acids (VFAs) in sewage is required. VFAs are the main product of organic matter hydrolysis from sewage sludge. However, no attention has been given to other products of the process. It has been found that in parallel to VFA production, toluene formation occurred. The formation of toluene in municipal anaerobic sludge digestion processes was investigated. Experiments were performed on a laboratory scale using sludge from primary and secondary settling tanks of municipal treatment plants. The concentration of toluene in the digested sludge from primary settling tanks was found to be about 42,000 μg/L. The digested sludge supernatant liquor returned to the biological dephosphatation and denitrification processes for sewage enrichment can contain up to 16,500 μg/L of toluene.