Hydroquinone is a widely used derivative of phenol which has a negative influence on human beings and the environment. The determination of the accurate amount of hydroquinone is of great importance. Recently, the fabrication of an electrochemical sensing device has received enormous attention. In this study, we reported on the facile synthesis of cerium dioxide (CeO2) nanoparticles (NPs). The CeO2 NPs were synthesized using cerium nitrate hexahydrate as a precursor. For determining the physicochemical properties of synthesized CeO2 NPs, various advanced techniques, viz., powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS), were studied. Further, these synthesized CeO2 NPs were used for the modification of a glassy carbon electrode (CeO2/GCE), which was utilized for the sensing of hydroquinone (HQ). A decent detection limit of 0.9 µM with a sensitivity of 0.41 µA/µM cm2 was exhibited by the modified electrode (CeO2/GCE). The CeO2/GCE also exhibited good stability, selectivity, and repeatability towards the determination of HQ.