As a modified configuration of the conventional anaerobic/anoxic/aerobic (AAO) process, a novel anoxic/ anaerobic/aerobic (Reversed AAO, RAAO) process has been extensively applied in domestic wastewater treatment plants (WWTP). In this study, the Activated Sludge Model No. 2d (ASM2d) and a secondary clarifier model were calibrated and applied to simulate a pilot-scale RAAO test and evaluate the operational performance of the RAAO process. For calibration of the biological model ASM2d, only four kinetic parameters were adjusted to accurately simulate in-process variations of ammonium, nitrate and phosphate. Simulation results by the calibrated model demonstrated that phosphorus accumulating organisms (PAO) in the RAAO process (0.243 gP·(gCOD)^(-1)) contains less poly-phosphate than the AAO process (0.266 gP·(gCOD)^(-1)). With the increasing mixed liquor recirculation ratio in the RAAO process, the fraction of heterotrophic biomass and autotrophic biomass both increased, whereas the PAO decreased owing to adverse effects of electron acceptors on phosphorus release and poly-hydroxy-alkanoates synthesis.