Identifying the operative mode of phase separation [spinodal decomposition (SD) or nucleation–growth (NG)] remains an extremely important area of research. The present work examines this critically in the Fe–Cr system using atom probe tomography (APT) and small angle neutron scattering (SANS), and establishes the framework to distinguish the two different modes of α′ phase separation in thermally aged Fe–35 at% Cr and Fe–20 at% Cr alloys. Independent APT analysis determines the mode of phase separation on the basis of (i) the presence/absence of periodic chemical fluctuation through radial distribution function analysis and (ii) interphase interface characteristics (diffuse/sharp). SANS analysis, in contrast, yields virtually indistinguishable correlation peaks for both the modes, which necessitates further investigation of the several different aspects of SANS profiles in the light of APT results. For the first time, key features of SANS profiles have been identified that can unambiguously distinguish SD from NG in the Fe–Cr system: (i) nature of temporal evolution of FWHM of the correlation peak and (ii) appropriate value of γ for fitting with the dynamic scaling model (γ = 6 for SD, Fe–35 at% Cr alloy; γ = 4 for NG, Fe–20 at% Cr alloy).