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In this paper, CeO₂ nanoparticles were synthesized by the solvothermal method and dispersed uniformly in graphene oxide (GO) aqueous solution by ultrasonication. The homogeneous CeO₂-GO dispersion was coated on the surface of a glassy carbon electrode (GCE), and the CeO₂/electrochemically reduced graphene oxide modified electrode (CeO₂/ERGO/GCE) was obtained by potentiostatic reduction. The results of X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) showed that CeO₂ nanocrystals were uniformly coated by gossamer like ERGO nanosheets. The electrochemical behavior of vanillin on the CeO₂/ERGO/GCE was studied by cyclic voltammetry (CV). It was found that the CeO₂/ERGO/GCE has high electrocatalytic activity and good electrochemical performance for vanillin oxidation. Using the second derivative linear sweep voltammetry (SDLSV), the CeO₂/ERGO/GCE provides a wide range of 0.04–20 µM and 20 µM–100 µM for vanillin detection, and the detection limit is estimated to be 0.01 µM after 120 s accumulation. This method has been successfully applied to the vanillin detection in some commercial foods.