In this work, to promote the cathodic and barrier performance of zinc-rich cycloaliphatic epoxy resin (ZRER) coatings containing 90 wt.% zinc dust particles, cerium oxide nanoparticles were used. The effect of CeO2 content 0–5 wt.% and the anticorrosion behavior of nanocomposite coatings were investigated by different techniques, including open circuit potential, electrochemical impedance spectroscopy, and salt spray tests. Results revealed that ZRER coatings containing 2 wt.% CeO2 nanoparticles had boosted sacrificial anode and barrier protection during immersion in a 3.5 wt.% NaCl solution. The addition of 2 wt.% CeO2 into the coating system significantly reduced corrosion products and blisters while increasing resistances from 72,443 Ω cm2 to 426,579 Ω cm2 compared with the control ZRER sample after 120 days immersion. This high-performance anticorrosion behavior of the nanocomposite coatings is mostly due to the CeO2 nanoparticles, which have the capability to moderate the zinc dissolution rate in addition to improving the barrier by filling porosity and creating tortuous paths.