In this contribution, the azo dye (E)-1-(4-((4-(phenylamino)phenyl)diazenyl) phenyl)ethanone (DPA) was combined with reduced graphene oxide (RGO) for the electrochemical modification of a pencil graphite electrode (RGO/DPA/PGE) surface. A series of electrochemical measurements were used for the characterization of the modified electrode surfaces. At the modified electrode, nicotine was irreversibly reduced. An obvious increase was observed in the reductive peak current of nicotine at the modified electrode, indicating the capability of the RGO/DPA composite to increase the electron transfer rate. The current was found proportional to the nicotine concentration in a range of 31 to 1900 μM, and the limit of detection (LOD) was calculated as 7.6 μM.