Amorphous iron-molybdenum-boron deposits were obtained by electroless plating with a metal couple made up of copper & aluminum sheets. The films were prepared on the copper sheet in a bath containing ferrous sulfate, sodium potassium tartrate, sodium hydroxide, potassium borohydride and sodium molybdate. The deposits have perfect chemical resistant and good surface appearance. The co-deposited element of Mo with the Fe and B atoms improved the glass formation ability (GFA) of the alloys and extended the glass-forming region (GFR) of B content to 6.63 to 30.1 at%. The aggregation of molybdenum atoms was found in the present specimens. The microhardness of the deposits increases with the increment of B content in the deposits, which may be attributed to the strengthening of partial bonds formed by overlapping s-p hybrid orbits of boron atoms with the s-p-d orbits of iron and molybdenum atoms. (C) 2013 The Electrochemical Society. All rights reserved.