Simulations of spinodal decomposition in an Fe-36 wt%Cr alloy at 773 K are performed by solving the non-linear Cahn–Hilliard equation, and the results are compared with atom probe tomography measurements. The influence of gradient energy coefficient, atomic mobilities and initial structure on the kinetics of spinodal decomposition is studied. It is shown that a proper initial structure, accounting for the thermal history above the miscibility gap, is crucial and enables predictive simulations of spinodal decomposition in Fe-Cr alloys.