A series of electroactive epoxy/amino-SiO2 nanocomposite materials containing conjugated segments of electroactive amino-capped aniline trimer (ACAT) unit were successfully prepared. First of all, the amino-modified silica (AMS) particles of similar to 50 nm in diameter were synthesized by performing the conventional base-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) in the presence of (3-aminopropyl)-trimethoxysilane (APTES) molecules. Subsequently, the AMS nanoparticles were blended into the epoxy ring-opening polymerization reactions between amino-terminated aniline trimer (ACAT)/T-403 and DGEBA, leading to the formation of electroactive epoxy resin-silica hybrid nanocomposites (EES). Furthermore, the redox behavior of as-prepared EES materials was identified by the electrochemical cyclic voltammetry studies. It should be noted that the as-prepared electroactive hybrid materials in the form of coating on cold-rolled steel (CRS) electrode were found to be much superior in corrosion protection over those of non-electroactive epoxy (NEE) and electroactive epoxy (EE) materials based on a series of electrochemical corrosion measurements in saline. The possible mechanism for the advanced enhancement of corrosion protection of EES coatings on CRS electrode could be interpreted as follows: (1) electroactive epoxy coatings may act as physical barrier coating; (2) redox catalytic capabilities of ACAT units existed in electroactive epoxy may induce the formation of passive metal oxide layers on CRS electrode, as further evidenced by SEM and ESCA studies; (3) well-dispersed AMS nanoparticles in EES matrix could act as effective hinder to enhance the oxygen barrier property of electroactive epoxy matrix, the result could be demonstrated by gas permeability analysis (GPA). Electroactive epoxy/SiO2 nanocomposites were identified by a series of electrochemical measurements such as corrosion potential (E-corr), polarization resistance (R-p), corrosion current (I-corr) and electrochemical impedance spectroscopy (EIS) studied in 5 wt% NaCl electrolyte. (C) 2011 Elsevier Ltd. All rights reserved.