Composites 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 6.68x10(6)cm(2) in 5 wt. % NaCl solution even after 288 h, compared to EP (4.26x10(5)cm(2)) 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. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4528-4533, 2013