Optimization of an acid chloride bath for electrodeposition of smooth Zn-Ni alloy on to mild steel was studied using thiamine hydrochloride (THC) as brightener. The influence of deposition current density, temperature, composition, and corrosion properties of Zn-Ni alloy coatings was investigated. The effect of bath composition and operating parameters on deposits characters like composition, micro-hardness, thickness and adhesions were tested. Under no conditions of current density employed in the present study, the anomalous type of co-deposition has changed to normal type. Electrolytically deposited Zn-Ni alloys were characterized by electrochemical AC and DC techniques. The experimental results revealed that coatings having ∼ 3.16 wt. % Ni at 3.0 A/dm2 was the most corrosion resistant. The better corrosion resistance at optimal current density was attributed to the formation of n-type semiconductor film at the interface using Mott-Schottky (M-S) analysis. The effect of THC on plating process was investigated through cyclic voltammetry techniques. X-ray diffraction (XRD) studies of the coatings showed the presence of γ-Phase with composition of Ni5Zn21, responsible for it extended orrosion resistance. The change in the surface morphology of the coatings, with current density was analyzed using scanning electron microscopy (SEM).