Phase separation by spinodal decomposition of body centered cubic Fe-Cr binary alloys to form isotropic fully interconnected nanostructures of Fe-rich α and Cr-enriched α′ phases typically on a scale of 2 to 10 nm is scientifically intriguing and technologically important. In aged dual-phase steels, it is the decomposition of the ferrite to form such α-α′ composition modulations that is primarily responsible for the increased ferrite hardness that contributes to embrittlement. The α′ structures are isotropic since the lattice constants of the two phases are almost identical and consequently the strain energy is small. In other spinodal systems larger strain energy leads to triaxially modulated structures aligned along <100> in cubic materials. A review of TEM characterization of spinodal alloys revealed that aligned structures had received the most attention, because they are more common and their characterization by TEM is more tractable.