Cu has recently received great interest as a potential candidate for glucose sensing to overcome the problems with noble metals. In this work, reduced graphene oxide-encapsulated Cu nanoparticles (Cu@RGO) have been prepared via an electrostatic self-assembly method. This core/shell composites were found to be more stable than conventional Cu-decorated graphene composites and bare copper nanoparticles in an air atmosphere because the graphene shell can effectively protect the Cu nanoparticles from oxidation. In addition, the obtained Cu@RGO composites also showed an outstanding electrocatalytic activity toward glucose oxidation with a wide linear detection range of 1 μM to 2 mM, low detection limit of 0.34 μM (S/N = 3), and a sensitivity of 150 μA mM-1 cm-2. Moreover, Cu@RGO composites exhibited a satisfactory reproducibility, selectivity, and long effective performance. These excellent properties indicated that Cu@RGO nanoparticles have great potential application in glucose detection.