In this study, we developed a novel molecularly-imprinted electrochemical sensor based on a glassy carbon electrode (GCE) decorated by graphene–Prussian blue (GR–PB) composites for the selective and sensitive determination of butylated hydroxyanisole (BHA). The molecularly-imprinted polymers (MIPs) were synthesized by BHA and pyrrole as the template molecule and functional monomer, respectively. Also, the MIPs were assembled on the surface of the GR–PB/GCE by electropolymerization. The sensor was characterized by cyclic voltammetry (CV), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and chronoamperometry. It was confirmed that the synergistic effects of GR and PB could improve the electrochemical response and the sensitivity of the sensor. The linear range of the sensor was from 9 × 10−8 mol L−1 to 7 × 10−5 mol L−1, with a limit of detection (LOD) of 7.63 × 10−8 mol L−1 (S/N = 3). The proposed sensor displayed high selectivity, excellent stability and good reproducibility for the determination of BHA. It was successfully applied to the determination of BHA in real samples.
