Anion-exchange membranes of bipolar membrane electrodialysis(BMED) which recovered organic acid from butyl-acrylate wastewater were studied. Performances of the membranes were analyzed before and after polluted by butyl-acrylate wastewater. Attenuated total reflection-Fourier transform infrared (ATR-FTIR), scanning electron microscopy-energy spectrum (SED-EDS) and X-ray photoelectron spectroscopy (XPS) were applied to characterize the composition changes of the membrane surfaces. Membrane performance results indicated that the used membranes were polluted with higher area resistance and lower transfer number than new membrane. EDS results indicated that membrane pollutants contained oxygen and carbon atoms, since the composition of carbon and oxygen atoms increased from 78.10% and 8.34% to 81.76% and 12.05%, respectively after the membrane was used. Results of C(1s) analysis of XPS spectra indicated that membrane pollutants contained —COO-Na+, because the composition of —COO-Na+ increased from 8.5% to 13.7% after the membrane was used. ATR-FTIR results indicated that the absorption at 1 561 cm-1, which was asymmetrical stretch vibration of —COO-M+ (M: metal), was enhanced after the membrane was used. The results verified XPS results. As sodium polyacrylate was one of the pollutants in butyl-acrylate wastewater, it was used to pollute anion-exchange membrane. And then, the polluted membrane was analyzed for performance, XPS spectral and ATR-FTIR spectral. The results indicated that polyacrylate resulted in membrane resistance increase, transfer number decrease, —COO-Na+ composition increase, and absorption enhancement at 1 561 cm-1. Therefore, sodium polyacrylate is an important pollutant which can result in pollution of anion-exchange membrane. Spectral methods are useful tools for characterization and identification of fouling pollutants on ion exchange membrane.