A sodium dodecyl sulfate modified carbon paste electrode (SDS/CPE) was developed in this work based on the surface modification method. The modified electrode was prepared by immersing SDS/CPE in a nickel nitrate solution. This electrode showed a strong accumulation ability toward nickel ions. Then modified electrode was conditioned by potential recycling in a potential range of 0.2–0.8 V (vs. Ag/AgCl/KCl) by cyclic voltammetry in alkaline medium. The results showed that the Ni/SDS on the electrode behaves as an efficient catalyst for the electrooxidation of methanol in alkaline medium via Ni (III) species formed on the electrode. Moreover, the effects of various parameters such as SDS concentration, methanol concentration, NaOH concentration and nickel nitrate concentration on the electrooxidation of methanol have also been investigated.