Mn–Co alloys were electroplated on AISI 430 stainless steel using an electrodeposition technique with the aim to reduce oxidation and chromium volatilization. The electroplating parameters were designed to improve the coating quality. The increased current density with decreased MnSO4 content resulted in a denser coating layer. A sample coated with 0.10 M CoSO4 and 0.50 MnSO4 at 350 mA cm−2 showed the best oxidation resistance after being oxidized at 800 °C for 90 h. The X-ray diffraction (XRD) result revealed that the oxide growth on the surface of the coated samples mainly formed oxides of MnCo2O4, MnCr2O4, and Cr2O3. The chromium volatilization was evaluated by exposing the coated samples to humidified synthetic air at 800 °C for 96 h. The mass flux of Cr volatilization was on the order of 10−11 g cm−2 s−1. Furthermore, different heat treatments in O2 and CO2 atmospheres were compared. Annealing in CO2 at 800 °C for 4 h helped increase the Mn–Co coating density. The relationship between the porosity and its failure behavior was also discussed.