Ionic transport behavior across an electropolymerized polypyrrole/polyazulene composite film was investigated by using ac impedance analysis, and its charge‐discharge characteristics were also studied. Co‐electropolymerization of pyrrole and azulene was well defined and fairly stoichiometric in propylene carbonate solution. The charge capacity for the composite films showed a remarkable increase for films with about 50 to 75% of azulene monomer content, and the behavior was correlated with morphological and diffusivity changes. The charge‐discharge characteristics were examined for cells with a lithium anode and various polypyrrole/polyazulene composite cathodes. Pure polypyrrole cathodes behaved exactly like a capacitor at low frequency, while pure polyazulene cathodes showed excellent rechargeable behavior with very flat discharge curves. Composite cathodes showed intermediate behavior.