In this paper, we report on the nucleation and the growth of heterogeneous Mn-Bi thin films on Cu substrate from a mixed sulfate-nitrate bath using direct current plating. The electrolytic bath is characterized by the presence of ammonium sulfate which was used as complexing agent to avoid the precipitation of Mn hydroxides. Cyclic voltammetry and chronoamperometry measurements are used to study the reaction mechanisms of the Mn-Bi electrodeposition as a function of the ammonium sulfate concentration and the pH value: the optimized conditions for a stable bath are obtained for 2.5 mol. L-1 of ammonium sulfate and pH 2.3. The Scharifker and Hills (SH) model was used to analyze the current transients at the initial stage of deposition; it was revealed that Mn-Bi electrocrystallization process is governed by three-dimensional nucleation. But as the electrochemical deposition clearly involves the simultaneous presence of the proton cathodic reaction, another model developed by Palomar-Pardave and co. was used to explain the nucleation mechanism and to describe the individual contribution of both the metallic ions and the proton reduction process. The morphology and chemical composition of the films were examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The deposits have a cauliflower-shaped appearance with a heterogeneous distribution of manganese and bismuth. The energy dispersive spectroscopy analysis reveals the presence of manganese and bismuth peaks with almost the same relative intensities. The X-rays diffraction analysis shows characteristic peaks of manganese and bismuth. (C) 2014 The Electrochemical Society. All rights reserved.