The synergic effect of the substituentlike ethoxy group on the electronic properties of conducting polyaniline was investigated. The presence of substituents affects not only the electrochemical polymerization window but also brings about changes in optical and electronic properties of the parent polymer polyaniline. The study indicates that electrochemical polymerization of (o-ethoxyaniline) yields a conducting polymer that shows a multiple color transition (yellow --> green) on switching the potential between the reduced and oxidized states with an electrochromic response time of 40 ms in addition to its solubility in dimethyl sulfoxide, N-methyl pyrrolidinone, etc. However, the chemical polymerization of the monomer yields a crimson red polymer that is less conducting but has solubility in ethanol/methanol. Evaluation of this alcohol soluble polymer as a corrosion inhibitor for iron in acidic medium shows that it offers corrosion inhibition efficiency of 90%.