Iron and iron-nickel alloy electrodeposits synthesized from sulfate-based electroplating baths were applied to a mild carbon steel substrate. Coated specimens were immersed in an oxygen-saturated, weak ammonium hydroxide solution (pH 9.5–10.0), and their corrosion performance was evaluated using electrochemical techniques. Galvanic and general corrosion behaviors were analyzed to assess the sacrificial protection provided by Fe and Fe-Ni coatings relative to uncoated steel. The influence of anode-to-cathode (A/C) surface area ratios (1:1, 10:1, and 100:1) on the occurrence of plating-induced surface cracks was also examined. Surface morphology and elemental composition of the deposits were characterized. Results of the study indicated that increasing the Ni²⁺/Fe²⁺ molar ratio of the electroplating bath from 0 to 0.167 led to (1) reduced surface porosity and cracking, (2) decreased galvanic corrosion rates between the electrodeposit and substrate, and (3) a progressive increase in the temperature dependence of the general corrosion rate between 20 °C and 60 °C. The development of Fe and Fe-Ni alloy electrodeposits as protective coatings is of particular interest in water-tube power boiler applications, where production of corrosion products must be controlled. Further research is needed to develop coatings that perform predictably under elevated pressures and temperatures typical of operating boiler environments.