The kinetics of Ni-Mo alloy electrodeposition on steel substrates from an aqueous citrate-ammonia complex baths has been investigated by means of steady-state polarisation measurements in a system with a rotating disc electrode (RDE). Partial current densities for discharge of Ni(II) and Mo(VI) ions and hydrogen evolution as a function of molybdate concentration in the bath, cathode potentials and the rate of mass transport were determined. It has been shown that - under all investigated conditions - Ni-Mo alloy deposition is more favourable than pure nickel and the cathodic process is strongly influenced by the Mo(VI) content in the solution. The Ni(II) electroreduction rate initially increases, as the cathode potential shifts towards more negative values and the concentration of molybdate grows in the solution. However, for the highest examined MoO42- content, a considerable decrease in the rate of the process is subsequently observed at certain limit potentials, the values of which depend on molybdate concentration and hydrodynamic conditions. This effect, related to the formation of intermediate molybdenum oxides (characterised by very low overvoltage for hydrogen evolution), becomes less pronounced when the RDE rotation speed is increased. Hydrogen evolution is strongly associated with molybdenum deposition. An increase of the molybdate ions concentration in the bath, as well as an increase in the rate of mass transport, leads to an increase in Mo content in deposits and to the reduction of current efficiency. The Ni-Mo coatings electrodeposited from the designed bath (with the current efficiency of about 70%) containing about 30 wt.% Mo, are characterised by a shiny-grey appearance and good adhesion to the steel substrate. They are characterised by column growth and amorphous microstructure with randomly distributed nanocrystallites of the MoNi4 intermetallic phase. (C) 2011 Elsevier B.V. All rights reserved.