The extracellular electron transfer (EET) efficiency in bioelectrochemical systems has been proven to be dependent on anode potentials. To explore the underlying mechanism, previous studies have mainly focused on EET conduit and bacterial biomass but rarely concerned with the role of extracellular polymeric substances (EPS) surrounding electroactive cells. In this study, the response of Geobacter biofilms to anode potentials was investigated with a special emphasis on the mechanistic role of EPS. The electrochemical activities and cell viabilities of Geobacter soli biofilms were simultaneously attenuated at 0.4 and 0.6 V compared to -0.2 and 0 V. It was found that the biofilms (especially the biofilm region closer to electrode surface) grown at -0.2 and 0 V produced relatively more extracellular redox-active proteins and less extracellular polysaccharides, which conferred higher electron accepting/donating capacities to EPS and consequently facilitated EET. Meanwhile, electrically nonconductive extracellular polysaccharide-dominated interior layers were formed in the biofilms grown at 0.4 and 0.6 V, which limited direct EET but might serve as physical barriers for protecting cells in these biofilms from the increasing stress by poised electrodes. These results demonstrated that the production of EPS under different anode potentials might be finely regulated by cells to keep balance between EET efficiency and cell-protection. This study provides a new insight to investigate the Geobacter biofilms coping with various environments, and is useful for optimizing electrochemical activity of anode biofilms.