An aqueous solution, acting as a photoinduced electron-transfer system, was prepared using tris(2,2′-bipyridyl)ruthenium complex, methylviologen, and pyrrole to demonstrate the multiphoton-sensitized polymerization of pyrrole. A conductive polypyrrole (2.7 × 10−2 S cm−1 in free standing state) was obtained on a glass substrate by illumination at 800 nm using a femtosecond pulses laser. The excitation of the ruthenium complex was entailed by two-photon absorption because the ruthenium complex did not have any absorption around 800 nm.