In this work, Mn–Bi system has been successfully electrodeposited on Cu/Si substrates from aqueous ammonium chloride containing electrolyte. A thermodynamic study of the electrolysis bath highlights the possible formation of manganese complexes (MnCl+, MnCl2, MnCl-) and bismuth complexes (BiCl 2+, BiCl2 +, BiCl3, BiCl4 -, BiCl5 2-, BiCl6 3-) The mechanism process involving Mn and Bi electrodeposition is investigated by cyclic voltammetry. Mn–Bi films can be grown under potentiostatic control. The physico-chemical, morphological and structural characterizations of the deposits were carried out by scanning electron microscopy (SEM) and X-rays analysis (XRD). The results reveal a granular surface quality and a heterogeneous chemical composition of the films. The energy dispersive spectroscopy (EDS) analysis reveals the presence of manganese and bismuth peaks whose relative intensities vary according to the imposed potential and the position on the sample. The X-rays diffraction analysis showed three different crystalline phases: α-manganese (body centred cubic system), γ-manganese (body centred tetragonal system) and bismuth (rhombohedral system).