We analyzed the role of exopolysaccharide in the Xanthomonas axonopodis pv. citri (Xac) Cu2+ resistance mechanism by Fourier transform infrared (FTIR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies. The FTIR data show that cells cultivated in the presence of 0.2 mmol L-1 of CuSO4 produce larger amounts of pyruvated exopolissacharide (EPS) than the ones cultivated in its absence. The EPR data indicate that the amount of Cu2+ decreases with cultivation time. The C-13-CPMAS NMR data also show the complexation of Cu2+ ions to the EPS. The results demonstrate that EPS plays an important role in Xac Cu2+ protection. Both capsular and slime EPS act as an initial protection mechanism, binding free Cu2+ ions, reducing their diffusion and their active transport to the cytoplasm. Cu2+ also induces the production of a highly pyruvated negative EPS, increasing its capture and binding capacity.