The characteristics of dissolved organic matter (DOM) such as chemical composition, molecular weight (MW) distribution and hydrophobic/hydrophilic distribution can affect wastewater treatment efficiency, effluent quality and ecological risk. Fluorescence spectroscopy could provide a quick estimate of DOM characteristics during the monitoring of wastewater treatment plants (WWTPs). In this study, the characteristic and quantitative correlation of DOM from 14 anaerobic-anoxic-oxic (AAO) processes of WWTPs located in different provinces (municipalities) of China were investigated. The results showed that DOM of MW <1 kDa was the largest group of DOM in influent and secondary effluent, and DOM removal increased as the MW increased. Hydrophilic (HPI) fraction and hydrophobic acid (HPO-A) comprised the major portion of DOM in influent and secondary effluent and exhibited the lowest rate of removal. In addition, DOM concentrations in the northern provinces were higher than in the southern provinces, which were related to the water quality, economy and population. There were positive correlations between specific fluorescence intensity (SFI) and the MW <1 kDa, 1–5 kDa and <10 kDa fractions. The smaller the molecular weight, the better the correlation. Strong positive correlations between regional fluorescence proportion (f_i) and HPI were found. SFI and f_i may be explored as potential indicators of the MW fractions and the hydrophobic/hydrophilic distribution of DOM in AAO processes WWTPs.