The spectral characteristic of dissolved organic matter (DOM) in Xiaohe River, Hebei, was investigated by fluorescence spectroscopy, ultraviolet-visible absorption spectroscopy, and basic chemical water quality indicators. The data was then statistical analyzed using principal component analysis and correlation analysis method. The result based on 3D excitation-emission matrix fluorescence spectroscopy showed that DOM in Xiaohe River contained both protein-like and humus-like components. DOM and N-containing compounds were obviously correlated with COD, especially between NH4+ -N and humic-like component, indicating that COD of water in Xiaohe River can be reduced by removing NH4+ -N and DOM, which could be good indicators for monitoring water quality in the future. The relative content of protein-like component reduces gradually along the downstream, while that of humic-like component showed an increasing trend. DOM in samples S1 and S2 was mainly consisted of humic-like components with larger molecular weight and higher aromaticity, while that in samples S3 and S6 was mainly consisted of protein-like components with smaller molecular weight, lower aromaticity, which are easier to be degraded. Therefore, in order to enhance the remove of refractory humic-like substances, sewage treatment plants of S1 and S2 or improved membrane treatment equipment with better removal effect of macromolecules should be provide. On the other hand, the anaerobic and aerobic biological treatment processes should be optimized in S3 and S6, so as to better remove these degradable protein-like substances.