The Cu-Mn based spinel coatings without Cr show good application prospects due to their high conductivity and thermal expansion coefficient matching with metallic interconnectors. Based on the Cu-Mn-O phase diagram, the CuMn alloy layers with different Cu/Mn ratios were designed by electro-deposition and high energy micro-arc alloying (HEMAA) processes. The Mn-33Cu-17Co layer was prepared by HEMAA for thermal growth of the CuMn spinel oxides, and the fine-grained 430 layer was prepared by HEMAA as an interlayer at the interface between the 430 SS substrate and the coating. The microstructure and composition of the composite layers were analyzed. The results show that after oxidation treatment at 750 °C for 500 h, the oxide products of the Mn-33Cu-17Co layer were mainly cubic spinel Cu1.4Mn1.6O4 and CuO, which were different from those of the Mn-35Cu oxide layer, spinel Cu1.2Mn1.8O4 and Mn2O3. The aggregation of Cu-rich oxides was not found in the cross-section and on the top surface of the Mn-33Cu-17Co oxide layer, and the outer spinel layer was uniform and compact. The designed Mn-33Cu-17Co layers, Mn-35Cu layers and Mn1.5Cu1.5 layers showed good high temperature oxidation resistance and electrical conductivity.