Understanding exoelectrogenic reactions of the bioanode is limited due to its complexity and the absence of analytics. Impedance and thermodynamics of bioanode, abiotic anode, and riboflavin-amended anode were evaluated. Activation overpotential of the bioanode was negligible compared with that of the abiotic anode. Impedance spectroscopy shows that the bioanode had much lower charge transfer resistance and higher capacitance than the abiotic anode in low frequency reaction. In high frequency reaction, the impedance parameters, however, were relatively similar between the bioanode and the abiotic anode. At open-circuit impedance spectroscopy, a high frequency arc was not detected in the abiotic anode in Nyquist plot. Addition of riboflavin induced a phase angle shift and created curvature in high-frequency arc of the abiotic anode, and it also drastically changed impedance spectra of the bioanode.