High conducting polyaniline films were readily prepared by in situ chemical oxidative polymerization/deposition of aniline in the presence of a very small amount of organic additive such as phenol. The conductivity of a thin (∼150 nm) polyaniline film synthesized in the presence of 0.01 wt % of phenol (r-PANI) is an order of magnitude higher (as well as better conducting homogeneity) than that of a film (PANI) obtained from the conventional method without an additive. r-PANI also has better adhesion and electrochemical stability/reversibility, more transparency in the visible-light region, and faster/easier doping/dedoping response compared to PANI. The function of phenol molecule is to avoid the formation of the inter- and/or intrachain hydrogen bonding during the growth of the polyaniline chains. The deaggregation/reducing intrachain hydrogen bonding of polyaniline chains by phenol molecules was revealed with IR, SAXS, and SEM data. All these data supported that phenol does assist the deaggregation of polyaniline chains during the growth of polymer chains or nanorods.