Ni-B/Ni-P-CeO₂ duplex coatings containing inner Ni-B layer were synthesized through the electrodeposition process. A mild steel sheet was used as substrate material to deposit the coatings. The structural, surface and electrochemical properties of the duplex coatings in their as synthesized condition were compared with Ni-P, Ni-B and binary Ni-B/Ni-P duplex coatings to demonstrate the improved performance of Ni-B/Ni-P-CeO₂ duplex coatings. The structural analysis (XRD) indicates that the developed coatings exhibit amorphous behavior. The SEM and AFM studies indicate that Ni-B/Ni-P-CeO₂ duplex coatings have less surface defects and more defined nodular structure compared to Ni-P, Ni-B and Ni-B/Ni-P duplex coatings. However, these coatings show an increase in surface roughness which may be attributed to the incorporation of CeO₂ ceramic particles used as reinforcement. The Ni-B/Ni-P-CeO₂ duplex coatings present superior anticorrosion properties compared to Ni-B and duplex Ni-B/Ni-P coatings. The improved electrochemical performance of novel Ni-B/Ni-P-CeO₂ duplex coatings can be regarded as the effect of less defective structure produced due to blocking of pores and reduction in the active area of the Ni-B/Ni-P matrix by the presence of CeO₂ ceramic particles. Owing to tempting properties, Ni-B/Ni-P-CeO₂ duplex coatings may be considered as potential candidate for oil and gas industry.