In this study, preparation and electrochemical corrosion protection studies of a series of polyimide Clay nanocomposite (PCN) materials were first presented. Subsequently, the as-prepared PCN materials were characterized by FTIR, XRD and TEM studies. In-situ monitoring for redox behavior of as-prepared PCN materials was identified by UV visible and CV studies. It should be noted that PCN coating was found to reveal advanced corrosion protection effect on cold-rolled steel (CRS) electrode as compared to that of neat non-electroactive polyimide coating based on series of electrochemical corrosion measurements in 5 wt% NaCl electrolyte. Enhancement of corrosion protection of PCN coatings on CRS electrode may be interpreted by following two possible reasons: (1) redox catalytic capabilities (i.e., electroactivity) of ACAT units existed in electroactive PCN may induce formation of passive metal oxide layers on CRS electrode, as evidenced by SEM and ESCA studies. (2) well-dispersed layered organophilic clay platelets embedded in electroactive PCN matrix could functioned as hinder with high aspect ratio to effectively enhance the oxygen barrier property of PCN, as evidenced by GPA. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.