Ni–Co alloys with varying cobalt content were electrodeposited employing sulphamate electrolyte. The changes in microstructure and corrosion behavior of electrodeposited nickel with respect to cobalt addition were studied. Scanning electron microscope, optical microscope and energy dispersive X-ray analysis were used to characterize the alloy coatings. The alloy co-deposition was observed to be anomalous type. The cross-section microhardness measurement indicated that the hardness reached the maxima for a cobalt content of 50 wt.% and then dropped with the increase in cobalt content. A correlation between microhardness and microstructure has been attempted. The optical micrographs indicated a change in microstructure from mixed columnar-fibrous to lamellar and finally to fibrous with increase in cobalt content. The X-ray diffraction (XRD) studies indicated the crystal structure to be cubic for cobalt content in the range of 0–50 wt.%. A transition to hexagonal structure was observed for a cobalt content of 70 wt.% and beyond. A change in preferred orientation was also observed with respect to cobalt addition. Potentiodynamic polarization and electrochemical impedance studies were used to study the corrosion behavior of Ni–Co alloys. The physical behavior was quantified with equivalent circuit. These studies indicated that the Ni–20% Co alloy exhibited better corrosion resistance in comparison to other Ni–Co alloys, plain nickel and plain cobalt coatings irrespective of the substrate (mild steel, brass) employed for deposition.