Ni59Zr20Ti16Si2Sn3 amorphous material was deposited by a vacuum plasma spraying technique onto steel and copper substrates in order to investigate their behaviour in a corrosive environment. For comparison, the same alloy was prepared as amorphous ribbons by melt spinning. The amorphous nature of the coatings and ribbons was characterized by XRD, DSC and TEM, while XPS and AES analyses were performed to understand the origin of passivation and mode of corrosion. The corrosion behaviour of the coating was studied in H2SO4 and HCl solutions open to air at room temperature. Potentiodynamic polarisation and galvanic coupling tests were carried out on the substrate and the coating. It was found that the formation of Zr-, Ti- and Si-rich passive oxide layers provide a high corrosion resistance in H2SO4 solution while the breakdown of the passive layer by chloride ion adsorption was responsible for pitting corrosion of the Ni59Zr20Ti16Si2Sn3 amorphous ribbons in HCl solution. Galvanic corrosion was the dominant corrosion mechanism for the coating/copper hybrid structure, in contrast to the Ni59Zr20Ti16Si2Sn3 amorphous coating, which efficiently protected the steel substrate in the corrosive environment.