[en] The effect of two non-complexing additives, namely Triton X₁₀₀ and 3-hydroxybenzaldehyde (3-HBA) on Zn-Mn alloy deposition was investigated. The study was carried out using a simple KCl-based bath. To this end, cyclic voltammetry associated to the switching potential method, bulk electrolyses and scanning electron microscopy were used. Electrochemical study, from additives-free bath, showed that the potential of beginning Zn-Mn alloy deposition (E = −1.52 V vs. Ag/AgCl) stands between those of Zn (E = −1.03 V) and Mn (E = −1.65 V) alloying elements. The coatings obtained from this bath are Mn-poor alloys with dendritic structure, and the current efficiency is low (60%). It was found that the conjunction of triton X₁₀₀ ad 3-HBA suppresses completely the individual electrodeposition of Zn. The synergistic effect of additives favors Zn and Mn co-deposition, but Mn-rich alloys are deposited only from E = −1.8 V vs. Ag/AgCl. The coatings obtained at lower cathodic potentials are adherent, smooth and bright. The current efficiency is enhanced and reaches 85%. Voltammogram data, from a comparative study using polyethylene glycol (PEG₈₀₀₀) instead of triton X₁₀₀, display prominently the vital role that plays the hydrophobic head of triton X₁₀₀ molecule in enhancing Mn incorporation into Zn matrix. Moreover, the switching potential technique demonstrated that at cathodic potentials higher than −1.8 V, the hydrogen evolution reaction is catalyzed when Mn-rich are deposited such that it gives rise to a higher pH increase at the cathode surface. This pH increase leads to an intense precipitation of hydroxides that blocks the alloy deposition process. - Highlights: • Investigation of Zn, Mn and Zn-Mn electrode position from an acidic chloride bath. • Synergistic effect of triton X₁₀₀ and 3-HBA on Zn-Mn electrochemical process. • Investigation of adsorption of the used additives at the cathode surface by Infrarouge. • Mn content is significantly enhanced in presence of both of Triton X₁₀₀ and 3-HBA.