Abstract: The process of cathodic reduction of zinc from alkaline zincate electrolyte was studied by cyclic voltammetry (CV), chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). The electrochemical nucleation mechanism of zinc in alkaline zincate system were studied by using chronoamperometry (CA) and scanning electron microscope (SEM) techniques. The results indicated that Zn existed in the electrolyte in the form of Zn(OH)42-, a preceding chemical transformation reaction existed in the electrodeposition process, and Zn(OH)2 was the species directly discharged on the cathode surface. Zn(OH)2 got two electrons by two steps on the cathode. The electrochemistry active middle product Zn(OH)ad was produced by the first reduction of Zn(OH)2 and adsorbed on the surface of cathode, and then was reduced to Zn by the second reduction. The two steps of reduction of Zn(OH)2 were all nonreversible reductions. It is helpful to the electrodeposition of Zn when the applied potential reduces. The system only occurred the first discharge reaction of Zn(OH)2 when the applied potential was at -1.40V ~1.50V. The two-step discharge reactions of Zn(OH)2 were both occurred in the alkaline zincate system, but Zn atoms only adsorbed on the cathode surface when applied potential reduced to -1.60V, and in this case, the electrodeposition process was in the non-steady state. The adsorbed Zn atoms could continuously migrate into the lattice and formed a uniform zinc plating only the applied potential reduces to -1.70V~-1.80V. The electrocrystallization of zinc from alkaline zincate electrolyte belonged to a three-dimensional progressive nucleation mechanism.