In order to investigate the mechanism of extracellular polymeric substances (EPS) influencing sludge characteristics, variations of extractable EPS from municipal sewage sludge by acid/alkaline pretreatment and gamma-ray irradiation were studied. The changes in constituents of EPS were analyzed by UV-vis spectra and SEM images. The effects of alkaline pretreatment and gamma-ray irradiation on the functional groups in EPS were investigated by Fourier transform infrared (FTIR) spectrometer. Results showed that the extractable EPS increased clearly with increasing irradiation dose from 0 to 15 kGy. UV-vis spectra indicated that a new absorption band from 240 nm to 300 nm existed in all irradiated samples, apart from acid condition. The results of FTIR spectroscopic analysis indicated that, irradiation influenced major functional groups in EPS, such as protein and polysaccharide, and these effects were clearer under alkaline condition. SEM images provided that after alkaline hydrolysis, gamma-ray irradiation was more effective in resulting in the sludge flocs and cells broken, compared with acid pretreatment (pH 2.50). (c) 2013 Published by Elsevier Ltd.