The integration of fuel cell device and supercapacitor device into a singular hybrid power source at the electrode level can make the best use of the advantages of each individual device and more importantly, eliminate the energy loss by virtue of the conversion of chemical energy to electric energy on electrocatalyst material and the storage of electric energy on energy storage material simultaneously. To avoid the use of noble metal electrocatalyst and exploit the dual electrocatalytic and capacitive function of polyaniline, a noble-metal-free fuel cell-supercapacitor hybrid power source employing polyaniline electrode as both anode and cathode is rationally constructed. Based on electrochemical in-situ Raman spectroscopy, this work proposes that the open circuit potential (OCP) of polyaniline electrode is a simple and quick indicator of the redox state of polyaniline. After carefully selecting the fuel and carbon-based support, it is found that the ascorbic acid fuel and the carbon fiber cloth supported polyaniline contributes to the lowest OCP threshold in the anode, and thus the fastest self-charge and largest stabilized open circuit voltage of hybrid power source. The hybrid power source can be self-charged to 0.32 V and yield a peak power density of 0.21 mW cm−2.