The traditional parameters of water quality, shuch as chemical oxygen demand (COD) and biological oxygen demand (BOD), only present total organic substance concentration and are void for displaying pollutant compositions. Fluorescence spectrum, a novel method for water quality, is unique for each wastewater sample like ‘fingerprint’. Excitation-emission matrix (EEM) technology is used to study fluorescence properties of municipal wastewater. The results show that there are four typical fluorescence zones in EEMs of municipal wastewater. Locations and intensities of fluorescence peaks of each zone and the ratio of intensities at λex=280 nm,λem=340 nm (fluorescence center of the 1st zone) and λex=225 nm,λem=340 nm (fluorescence center of the 2nd zone) could exhibit main fluorescence features. Fluorescence fingerprint contains a great deal of pollutant information. By comparing EEMs of typical pollutants, the main fluorescence substances of wastewater are approximately identified. Fluorescence fingerprint method can present organic substance as well as their content and is well complementary to COD and BOD.