Tannery industry is one of the major traditional industries and important wastewater sources in China. The existing research mainly focus on the quality of inlet and outlet water, rather than the purification and transformation behavior of dissolved organic matter (DOM) in the treatment process of tannery wastewater. The UV spectra and fluorescence spectroscopy were used to detect the spectral characteristics of water samples in the treatment process, and it is analyzed that the formation process and the linear relationships between total fluorescence intensity and parameters. The results showed: the UV absorbance of DOM in wastewater increased firstly and then decreased with longer wavelength, and the wave peaks were found around the wavelength of 230 nm. The values of A253/A203 and SUVA254 increased firstly and then decreased, indicating the complex reaction process related to free substituent and aromatic rings. The fluorescence peaks appeared at the regions of λex/em=320～350/440～460 and λex/em=270～300/390～420, referred as visible humic-like and visible fulvic-like fluorescence, respectively. With the treatment process of tannery wastewater, the following fluorescence phenomenon were monitored, such as the blue-shift of humic-like fluorescence peak in the hydrolytic acidification tank, the appearance of tryptophan fluorescence peak in the second biochemical pond (λex/em=290/340), the weak fluorescence peak in the fourth biochemical pond (λex/em=350/520) and the stabilized fluorescence characteristics in the secondary sedimentation tank and water outlet. The achievements are helpful to investigate the degradation and formation behavior of water components, and significant for the fluorescence variation analysis in the treatment system. The removal rate of total fluorescence intensity of tannery wastewater fit better the removal rate of TOC with coefficient of r 0.835 5. The UV spectra and 3D-EEMs are effective to reveal the purification behavior and mechanism of tannery wastewater.