Hg(II), as an extremely hazardous heavy metal contaminant in the environment, poses a significant potential hazard to human health and ecosystems. A GR-MWCNTs-COOH/CeO2/Nafion composite film-modified glassy carbon electrode was prepared using the drop-casting method in this study. The GR-MWCNTs-COOH/CeO2/Nafion/GCE was electrochemically investigated through cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). Additionally, the surface morphologies of the composite film were evaluated using scanning electron microscopy (SEM). The conditions, such as buffer solution, pH, deposition potential, deposition time, modified film thickness, and Nafion content, were optimized. Under optimal experimental conditions, a good linear relationship between the peak current response of Hg(II) and its concentration in the range of 5–100 μg·L−1 was observed, with a detection limit of 0.389 μg·L−1. When it was used to detect Hg(II) in offshore seawater, the recovery rate ranged from 94.72% to 103.8%, with RSDs ≤ 5.79%.