In order to guarantee the running effect of Guodian Shenyang North Wastewater Treatment Plant, based on excitation-emission matrix (EEM) fluorescence spectroscopy, fluorescence regional integration (FRI) and material balance are used to evaluate the dissolved organic matter removal performance of modified A2O process. The results suggest that the albuminoid matters are the dominant components in modified A2O process influent, and there is small amount of fulvic-like materials. The removal efficiencies of the normalized integral volume of region Ⅰ, Ⅱ and Ⅳ are 81.5%, 54.0% and 63.4%, respectively, while the removal performance of normalized integral volume of region Ⅲ and Ⅴ is low, and the removal efficiencies are 30.2%, 27.8%, respectively. The calculation of material balance shows that pre-anoxic and anaerobic zones are mainly used for the material removal in the region Ⅰ and Ⅳ. Anoxic zone is mainly used for material removal in the region Ⅰ. Aerobic zone could remove material in all regions. In addition, normalized integral volume of region Ⅳ and the soluble chemical oxygen demand have nice linear correlation, and the correlation coefficient R2 is 0.991 1. The normalized integral volume of region Ⅳ can better reflect the variation trend of soluble chemical oxygen demand in modified A2O process.