The atom probe field-ion microscope has been used to study the diffusion at interfaces in metallic multilayers deposited directly onto field-ion specimens and to develop models for the solid state reactions occuring at the atomic-scale in multilayer systems. Results are presented for the low temperature annealing of a Co-Ni multilayer. Intermixing over about 2 atomic planes is found even in as-deposited samples, extending to mnm after heating at 300°C for 1 hour. Using atom probe results from bulk alloys, a Monte Carlo simulation has been developed for the Fe-Cr system, in which a miscibility gap exists, and is being used in an attempt to model the behaviour of interfaces in Fe-Cr multilayers. Preliminary results are presented, showing that interfaces which are initially mixed over 10 atomic planes become sharper by an ‘interface spinodal’ reaction.