The electrodeposition of the Fe-Ni powders from citrate containing electrolytes for different Ni/Fe ions concentration ratios, using Fe(Ill) and Fe(II) salts at pH 4.5 and pH 4.0 respectively was investigated by the polarization measurements and cyclic voltammetry. The morphology and composition of the electrodeposited powders were investigated by SEM and EDS analysis. The EDS analysis of the alloy powders confirmed anomalous co-deposition of Fe and Ni from both solutions, with the one obtained using Fe(III) salt being more pronounced. The morphology of electrodeposited powders was found to depend on the Ni/Fe ions concentration ratio, as well as on the valence of Fe ions used. A common characteristic for all powder samples was the presence of cone shaped cavities and nodules, while for the ratio Ni/Fe = 9/1 in both electrolytes pagoda like crystals, corresponding to the FeNi3 single crystal, have been detected. In the case of Fe(III) containing electrolytes current efficiency for powder electrodeposition was very small (about 1-2%) due to the first step in the electrochemical reaction being reduction of Fe(III) into Fe(II), while in the case of Fe(II) containing electrolytes current efficiency for powder electrodeposition varied between about 15% and 8% depending on the Ni/Fe ratio. (C) 2009 Elsevier Ltd. All rights reserved.