Direct electroless deposition, i.e., without using a sacrificial anode or substrate activation, of iron-boron (FeB) films on copper substrates is reported. Electroanalytical techniques including polarization measurements of oxidation and reduction half-reactions are employed to optimize process parameters, thereby enabling direct nucleation and sustained growth of electroless FeB films on copper. Scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction are used to characterize the film morphology, the deposition rate, the deposit composition and crystallinity. Optimized electroless FeB films have a growth rate of 0.24 mu m/hr, are smooth and amorphous, and exhibit acceptable corrosion resistance. (C) 2014 The Electrochemical Society. All rights reserved.