In the present study, we suggest a new way to reactivate performance of direct formic acid fuel cell (DFAFC) and explain its mechanism by employing electrochemical analyses like chronoamperometry (CA) and cyclic voltammogram (CV). For the evaluation of DFAFC performance, palladium (Pd) and platinum (Pt) are used as anode and cathode catalysts, respectively, and are applied to a Nafion membrane by catalyst-coated membrane spraying. After long DFAFC operation performed at 0.2 and 0.4 V and then CV test, DFAFC performance is better than its initial performance. It is attributed to dissolution of anode Pd into . By characterizations like TEM, Z-potential, CV and electrochemical impedance spectroscopy, it is evaluated that such dissolved ions lead to (1) increase in the electrochemically active surface by reduction in Pd particle size and its improved redistribution and (2) increment in the total oxidation charge by fast reaction rate of the Pd dissolution reaction.