Multi-photon sensitized polymerizations of pyrrole were carried out on various substrates to study the difference in the surface condition for the polymer deposition. The minimum resolution of 780nm for the polymer deposition was achieved by adoption of Nafion-coated substrate instead of bare glass substrate. It is a drastic improvement of the resolution for diffraction limit of 1.22μm. Since the polymer nucleation and the polymer growth were accelerated with the additional polymer layer, the fine patterns were obtained by lower energy photoillumination.