This review, which is divided into three parts, concerns electrochemical synthesis, spectroscopic characterization, and formation mechanisms of poly(o-aminophenol) (POAP) film electrodes. The first part of this review is devoted to describe the electropolymerization process of o-aminophenol on different electrode materials and in different electrolyte media by employing both potentiodynamic and potentiostatic methods. The second part refers to spectroscopic studies carried out by different authors to both, identify the products of the o-aminophenol electrooxidation and elucidate the chemical structure of poly(o-aminophenol) film electrodes. The third part shows the different mechanisms formulated to interpret the POAP films formation from both acid and basic solutions of o-AP. Also, some electrochemical and spectroscopic data which allowed to propos the corresponding formation mechanisms, especially in basic media, are described. 1. Introduction Oxidation of o-aminophenol on different electrode materials (gold, platinum, carbon, indium-tin oxide, etc.) in aqueous medium was shown to form poly-o-aminophenol (POAP). Like aniline, o-AP can be polymerized electrochemically in acidic, neutral, and alkaline solutions. However, while a conducting film is only formed in acidic media, POAP synthesized in neutral and alkaline media leads to a nonconducting film. Electropolymerization of o-AP in acid medium yields an electroactive polymer that exhibits its maximal electroactivity within the potential range ？0.2？V < E < 0.5？V (versus SCE) at pH values lower than 3 [1, 2]. The electroactivity of POAP was explained by a redox mechanism that involves an addition/elimination of protons coupled with a reversible electron transfer [2]. The charge-transport process at POAP films was studied by employing different electrochemical techniques [1–7]. In previous work [8], we studied the electrochemistry of POAP in the presence of different active redox couples in solution, and it was demonstrated that external variables, such as film thickness, solution pH and redox-couple concentration in solution, affect both the permeation process of electroactive species and the electron motion through a POAP film. An interesting review concerning charge-transfer and charge-transport processes occurring in the curse of redox reactions of POAP film electrodes can be found in [9]. The properties of POAP synthesized in basic medium are favorable to its applications in the field of bioelectrochemistry and electrocatalysis. In this regard, a nonconducting material is obtained that exhibits
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