NiFe/Cu multilayer stacks of 2 nm single layer thickness were deposited onto needle-shaped W tips by ion beam sputtering and analysed by atom probe tomography (TAP) after appropriate heat treatments. After annealing at 250°C for 30 min, no significant structural or chemical transformation of the initial layer system is detected, although such a heat treatment appreciably reduces the magneto resistivity. A slight decrease of the concentration slope at the interfaces is attributed to a very short-range interdiffusion. Clear grain boundary diffusion is observed after annealing at 400°C for 30 min. Further annealing at 500°C for 20 min and 40 min still preserves the layered structure with a homogeneous solution of Ni inside the Cu layers of up to 25 at.% Ni.