The influence of glycine, as a chelating agent, and triblock copolymer mixture of PPG-PEG-PPG and PEG1000, as a suppressor agent, on the deposition mechanisms of zinc and zinc-nickel alloys were studied by cyclic voltammetry (CV) and potentiometric electrochemical impedance spectroscopy (PEIS), using electrolyte solutions of chlorinated acid. Cyclic voltammetry measurements show that the composition of the electrolytic solution affects the voltammogram profiles. Complementary PEIS investigations allowed the electrodeposition mechanisms to be highlighted depending on the composition of the electrolytic solution. The electrodeposition of zinc, in the absence of additives, occurs in a single cathodic wave from the ZnCl3− species, whereas in the presence of glycine, a second more cathodic reduction wave is relative to the Zn(Gly)22+ species. The presence of the PPG-PEG-PPG and PEG1000 triblock copolymer induces a clear inhibition of the zinc reduction. Nevertheless, the zinc electrodeposition follows a three-dimensional instantaneous nucleation. The zinc electroplating mechanism involves a capacitive semi-circle at high frequency and two inductive loops at medium and low frequencies assigned to two adsorbed intermediates onto the substrate whatever the electrolyte composition. The presence of the polymer mixture affects the zinc reduction by increasing the charge-transfer resistance and the adsorption phenomena on the substrate. The electrodeposition of zinc-nickel alloys reveals a single reduction wave, from ZnCl3− and Ni(Gly)2+ species, and multiple anodic signals depending on the electrolytic composition, according to the presence of glycine to chelate the nickel species. The zinc-nickel electroplating was evidenced to be a multiple-step process with a three-dimensional instantaneous nucleation, including intermediate species adsorbed onto the substrate. The equivalent circuit proposed consists of two capacitive half-circles separated by an inductive loop for any electrolytic solution. However, the impedance spectra were affected by the presence of glycine by modifying the inductive loop reflecting the first adsorbed intermediate (Ni(I)ads). The morphology of zinc and zinc-nickel, with a nickel content between 14 and 19 wt%, is affected by the electrolyte composition, however with the same crystal lattice. The preferential orientation of the lattice was shown to depend on the additives present in the solution.