ASPEN PLUS, a steady-state simulator, was used in this study for predicting emissions of VOCs and tracing the fate of all compounds in biodegradation processes. Mathematical models for the processes such as volatilization, reaction and clarification were adopted from literatures. Unlike most previous simulations that various pollutants were considered as a single component, COD or BOD, four components of water, biomass, VOCs and COD were included in this simulation. Sensitivity analysis of several physical parameters on the performance of the WWTP was conducted. Model predictions of VOCs emissions agreed well with the plant data. The simulator could provide design conditions for a future WWTP as well as monitoring/control regimes to an existing WWTP.