Hydrolysis is an important process in biological wastewater treatment and is known to be the rate-limiting step in organic carbon removal from municipal or industrial wastewater. The influence of the readily biodegradable chemical oxygen demand fraction in biological wastewater treatment systems has been extensively investigated, but little is known about the effects of slowly biodegradable substrate (XS) on denitrification and enhanced biological phosphorus removal. The biodegradation of XS is initiated by hydrolysis, which is an integral part of activated sludge models, such as the Activated Sludge Model no. 2d (ASM2d). This process is slower than heterotrophic growth and thus becomes the rate-limiting step for the biodegradation of organic compounds. The aim of this study was to evaluate different concepts of modeling the hydrolysis process using the original and modified version of ASM2d. Batch test results obtained at a large biological nutrient removal (BNR) plant in Gdansk (Poland) provided an experimental database for comparison of the two model predictions. Both models were compared in terms of their predictions for the most important process rates in BNR activated sludge systems. In comparison with the orginal ASM2d, the modified model had no or only minor effect on the predicted nitrate utilization rate, phosphate release rate and anoxic/aerobic phosphate uptake rate, but better predicted the oxygen uptake rate. The average ARDs (average relative deviations) were 19.0 and 29.3% (original ASM2d) vs. 13.4 and 20.4% (modified ASM2d), respectively, for the settled wastewater without pretreatment and after coagulation–flocculation.