The formation mechanism of Polyaniline was derived from the post reactions of the polymerization intermediate. The intermediate, RPAN, (3000 angstrom thickness film, purplish-blue in color) was isolated on silane modified substrates after polymerization for 10 minutes. Under air, RPAN converts to emeraldine salt within a couple of seconds. In the inert atmosphere, the conversion occurred at a relatively low speed. In acidic media, the intermediate was believed to be a very reactive radical cation, which oxidized then coupled with aniline oligomers to start the auto-catalytic chain growing process. When the radical cation was quenched in water or acid, a violet species, IPAN, with a structure composed mostly of pernigraniline units, was formed. IPAN reacts slowly with aniline oligomers in the presence of protons and oxidants to emeraldine. The conversion processes were monitored by IR and Uv/Vis/NIR spectroscopy.