AbstractA new nanocomposite containing Ni(II) ions, electrochemically reduced graphene oxide (ERGO) and poly (p‐aminobenzenesulfonic acid) (Pp‐ABSA) on pencil graphite electrode (PGE) was prepared using electrochemical deposition coupled with self‐assembly accumulation method and characterized with different techniques. The electrochemical behavior and electrocatalytic activity of modified PGEs were investigated. The Ni/Pp‐ABSA/ERGO/PGE showed a unique electrocatalytic oxidation through an Electrochemical‐Chemical (EC’) pathway for methanol in alkaline media (Jpf=7.04 mA cm−2 and Eonest=0.38 V) compared to Ni/PGE, Ni/Pp‐ABSA/PGE and Ni/ERGO/PGE. The obtained results showed that the self‐assembled incorporation of Ni(II) ions in Pp‐ABSA/ERGO film prepared on PGE surface produced a stable modifier with high electrocatalytic activity towards methanol oxidation. In conclusion, the introduced method for the preparation of Pp‐ABSA/ERGO‐based nanocomposites can open a new, cheap and simple way to design a high‐performance electrocatalyst for direct methanol fuel cell systems.