Poly(N,N-dimethylaniline) (PDMA) was formed by successive cyclic voltammetry in monomer solution in the presence of sodium dodecyl sulfate (SDS) on the surface of a carbon paste electrode. The polymerization behavior of N,N-dimethylaniline in the presence of SDS is quite different from that of N,N-dimethylaniline in the absence of SDS. The effect of varying amount of SDS on the rate of polymerization of N,N-dimethylaniline was investigated. The electrochemical behavior of the SDS-PDMA carbon paste electrode has been investigated by cyclic voltammetry in 0.5 M H2SO4 and 5 mM K4[Fe(CN)6]/0.1 M KCl solutions as the supporting electrolyte and model system, respectively. The synthesized PDMA was characterized by FT-IR and scanning electron microscopy (SEM). Ni(II) ions were incorporated into the electrode by immersion of the polymeric modified electrode having amine groups in 0.1 M Ni(II) ion solution. The electro catalytic oxidations of methanol at the surface of the Ni/SDS-PDMA electrode were studied in a 0.1 M NaOH solution. Compared to bare carbon paste and PDMA-modified carbon paste electrodes; the SDS-PDMA electrode significantly enhanced the catalytic efficiency of Ni ions for methanol oxidation.