The chemical diffusion in thin trilayer films of TM–TM100−xZrx–TM with an amorphous middle layer where TM = Co, Ni, or Fe and in amorphous Fe–Zr and Ni–Zr films with composition gradients has been investigated using Rutherford backscattering spectrometry. The growth of the amorphous layer in the trilayers, due to in-diffusion of cobalt and nickel, is initially found to be proportional to the square root of the time, t1/2, and subsequently found to level off before the compositions corresponding to metastable equilibria are reached. Irradiation, with 500 keV Xe+ ions, is found to promote the in-diffusion. This behavior is discussed in terms of structural relaxation effects and their influence on the metastable equilibrium. In amorphous Fe–Zr the chemical diffusivity is observed to be very sluggish. Contrary to the behavior in Co–Zr and Ni–Zr trilayers, the direction of the iron diffusion in Fe–Zr trilayers suggests a broad positive peak in the Gibbs free energy at a composition around 50 at. % Zr. It is argued that the sluggish chemical diffusivity of iron is directly related to the unusual composition-dependence of the Gibbs free energy for amorphous Fe–Zr.