In this paper, the degradation of carbofuran with graphene oxide–ferroferric oxide–hemoglobin (GO–Fe3O4–Hb) composite in an electrochemical–enzyme system was reported. The graphene oxide–Fe3O4–hemoglobin composite was fabricated by a two-step process. First, graphene oxide–Fe3O4 (GO–Fe3O4) composite was prepared via a simple and effective chemical precipitation method. Then, hemoglobin was covalently immobilized onto the graphene oxide–Fe3O4 by glutaraldehyde (GA). The GO–Fe3O4–Hb composite showed improved enzyme thermal stability and wider active pH range compared with Fe3O4–Hb and soluble Hb. Furthermore, the GO–Fe3O4–Hb composite can be easily separated under a magnetic field from the reaction solution and reused. To evaluate the electro-enzymatic degradation of carbofuran, electrolytic experiments were carried out with 1U/mL GO–Fe3O4–Hb composite at 0.007A, and oxygen flow rate 25mL/min. Under the optimum conditions by the electrogeneration of hydrogen peroxide (H2O2), the removal efficiency of carbofuran reached 94.6%. Compared with electrochemical and biochemical methods, the removal of carbofuran through electroenzymatic method was comparatively favorable.