As the compositions of traditional Ni-Fe alloy coatings generated by the co-deposition of Ni and Fe could not be modulated easily, a novel method for preparing a new Ni-Fe alloy coatings having controllable components was proposed, namely the alloying of compositionally modulated Ni/Fe multilayer films. The surface and cross-section morphologies of compositionally modulated Ni/Fe multilayer films before and after the alloying were examined by a field emission scanning electron microscopy, and the element distribution of the new Ni-Fe alloy coatings prepared by the alloying of compositionally modulated Ni/Fe multilayer films was analysed using an energy dispersive X-ray analyser. The results showed that the distribution of elements in the new Ni-Fe alloy coatings was uniform. Moreover, the magnetic properties of the new Ni-Fe alloy coatings were investigated and the results showed that the magnetic performances of the new Ni-Fe alloy coatings differed from those of the traditional Ni-Fe alloy coatings.