A model is developed for analysing growth of intermediate (amorphous) phase and formation of solid solution along both the interfaces and the grain boundaries in multilayers. The model is valid up to moderate stages of isothermal annealing, when the multilayer can be conceived as a stack of infinite diffusion couples. Continued amorphization along the grain boundaries implies that fast diffusion paths remain active in the amorphous phase. The model is applied to experimental data obtained for Ni–Ti and Ni–Ta multilayers, showing solid state amorphization and solid solution formation. The chemical diffusion coefficient of the amorphous phase, Dam, is much smaller in the Ni–Ta system than in the Ni–Ti system, resulting in (i) less amorphization, and (ii) a much larger ratio of the grain‐boundary diffusion coefficient, Dgb, and Dam in Ni–Ta.