Display omitted •A high quality Cu/GO nanohybrid was fabricated via a facile one-step reduction method.•The Cu/GO nanohybrid displays excellent electrocatalytic property for the oxidation of 2-NAP.•The Cu/GO electrode displays super comprehensive performances for the detection of 2-NAP.•This proposed method was successfully applied to detect 2-NAP in water samples. A copper nanostructures-graphene oxide (Cu/GO) hybrid as a new electrocatalyst for highly sensitive detection of 2-naphthol (2-NAP) was successfully synthesized by a one-pot and in situ chemical reduction approach. The characterization results reveal that the cubic Cu nanostructures are tightly attached onto the GO sheets in the resulting hybrid. A lower oxidation potential and a larger peak current were observed for the 2-NAP oxidation at the Cu/GO modified electrode, demonstrating the synergistic electrocatalysis from Cu nanostructures and GO sheets. Consequently, the Cu/GO hybrid exhibits a low detection limit (5.0nM) and wide linear ranges (0.1–4.0μM and 4.0–130.0μM) when used as a sensing material for the sensitive detection of 2-NAP. Finally, the fabricated sensor was successfully applied in the detection of 2-NAP in real samples and satisfactory recoveries in the range of 99.3%–104.0% were achieved.