ABSTRACTComposites of Poly(2,3‐dimethylaniline) and inorganic Na+‐montmorillonite clay were synthesized by emulsion polymerization. The as‐synthesized composites (PDMA) were characterized by Fourier Transform Infrared Spectroscopy, X‐ray diffraction, and scanning electron microscopy. The protective performance against corrosion of the samples was evaluated by Tafel and electrochemical impedance spectroscopy measurements. The results showed that the composite containing 5 wt. % of clay loading (PDMA‐5%) displayed a better anticorrosive performance than other samples. The Epoxy(E) blend with PDMA‐5% (EPM5) coating was founded to have a higher corrosion potential and a lower current density than that of Epoxy blend P(2,3‐DMA) (EP) coating. The impedance value of EPM5 coating was about 6.68×106Ω·cm2 in 5 wt. % NaCl solution even after 288 h, compared to EP (4.26×105Ω·cm2) coating, which went to show that the corrosion inhibition of P(2,3‐DMA) could be effectively enhanced by incorporating MMT into the P(2,3‐DMA) matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4528–4533, 2013