Spinodal decomposition (SD) is an important phenomenon in materials science and engineering. For example, it is considered to be responsible for the 475 degrees C embrittlement of stainless steels comprising the bcc (ferrite) or bct (martensite) phases. Structural characterization of the evolving minute nano-scale concentration fluctuations during SD in the Fe-Cr system is, however, a notable challenge, and has mainly been considered accessible via atom probe tomography (APT) and small-angle neutron scattering. The standard tool for nanostructure characterization, viz, transmission electron microscopy (TEM), has only been successfully applied to late stages of SD when embrit-dement is already severe. However, we here demonstrate that the structural evolution in the early stages of SD in binary Fe-Cr, and alloys based on the binary, are accessible via analytical scanning TEM. An Fe-36 wt% Cr alloy aged at 500 degrees C for 1, 10 and 100 h is investigated using an aberration-corrected microscope and it is found that highly coherent and interconnected Cr-rich regions develop. The wavelength of decomposition is rather insensitive to the sample thickness and it is quantified to 2, 3 and 6 nm after ageing for 1, 10 and 100 h, which is in reasonable agreement with prior APT analysis. The concentration amplitude is more sensitive to the sample thickness and acquisition parameters but the TEM analysis is in good agreement with APT analysis for the longest ageing time. These findings open up for combinatorial TEM studies where both local crystallography and chemistry is required.