Poly(2

3-dimethylaniline)(P(2

3-DMA)) was synthesized by a rapid emulsion polymerization using ammonium peroxydisulfate and ferrous ion (APS/Fe2+) as composite oxidants.The effect of Fe2+ on the rate of polymerization of 2

3-dimethylaniline (2

3-DMA) was discussed by open circuit potential (OCP) curves

and the molar ratio of APS and Fe2+ and the amount of composite oxidant were optimized by cyclic voltammetry and Tafel curves.And the characterization results of electrochemical properties of P(2

3-DMA) were proved by contrast analysis of infrared spectroscopy (FTIR) and X-ray diffraction (XRD).The experimental results showed that main infrared absorption peaks of P(2

3-DMA) which was synthesized by the composite oxidant exhibited red-shift.The phenomenon revealed that the structure of products was relatively complete and the electron delocalization increased.The optimal properties of P(2

3-DMA) were achieved when the molar ratio of APS to Fe2+ was 10∶1

the molar ratio of APS to 2

3-DMA was 3∶1.The open-circuit potential measurements indicated that the rate of polymerization of 2

3-DMA with the aid of Fe2+ had a substantial increase.The P(2

3-DMA) with higher yield

better electrochemical and crystal properties have been prepared by composite oxidant APS/Fe2+.