Through extracellular electron transfer (EET), bacteria are capable of transforming different insoluble materials of geochemical interest into energy-rich molecules for their growth. For this process, bacteria have been depending directly or indirectly on molecules synthesized within the cells or by various synthetics as mediators. Herein, we studied the in-situ change in electrochemistry and supporting components for EET in the extracellular polysaccharide (EPS) producing biofilm of thermophilic Geobacillus sp. The CV and DPV resultsrevealed that the intact biofilm of bacteria was not able to generate any potential at 25 °C /- ≤50 °C. However, at 55 °C (optimal condition), the potential occurred drastically after the EPS production by bacteria. HPLC and MALDI-TOF results revealed that the presence of Flavins, which can able adsorbed to the electrodes from the cell surface. Moreover, the temperature-dependent EPS production and originally conceived ability of flavins to act as electron shuttles suggest that not much complexity in bacteria with minerals. Additionally, the electrochemical potential was severely affected upon removal of EPS/flavin moiety from the intact biofilm, revealed the necessity of EPS bound flavins in transferring the electrons across its thick cell walls. This paradigm shift to electrogenic nature of Geobacillus sp. biofilm will become evident in the adaptation of other microbes during mineral respiration in extreme environments.