The aim of this study was to evaluate the interaction between extracellular polymeric substances (EPS) and Zn (II) during the sorption process of Zn (II) onto aerobic granular sludge. Batch results showed that the adsorption rate of Zn (II) onto aerobic granular sludge was better fitted with pseudo-second order kinetics model, and the adsorption isotherm data agreed well with Freundlich equation. Extracellular polymeric substances (EPS) for Zn (II) binding during sorption process was investigated by using a combination of three-dimensional excitation-emission matrix (3D-EEM), synchronous fluorescence spectra, two-dimensional correlation spectroscopy (2D-COS) and Fourier transform infrared spectroscopy (FTIR). Results implied that the main composes of EPS, including polysaccharide (PS) and protein (PN), decreased from 5.92 +/- 0.13 and 23.55 +/- 0.76 mg/g SS to 4.11 +/- 0.09 and 9.55 +/- 0.68 mg/g SS after the addition of different doses of Zn (II). 3D-EEM showed that the intensities of PN-like substances and humic-like substances were obviously decreased during the sorption process. According to synchronous fluorescence spectra, the quenching mechanism between PN-like substances and Zn (II) was mainly caused by a static quenching process. Additionally, 2D-COS indicated that PN-like substances were more susceptible to Zn (II) binding than humic-like substances. It was also found that the main functional groups for complexation of Zn (II) and EPS were O-H groups, N-H groups and C=O stretching vibration. The findings of this study are significant to reveal the fate of heavy metal during its sorption process onto aerobic granular sludge through EPS binding, and provide useful information on the interaction between EPS and heavy metal. (C) 2015 Elsevier B.V. All rights reserved.