Arrays were self-assembled by evaporating suspensions of 4 nm FePt or 8 nm Fe nanoparticles. The monolayers had a hexagonal close packed (hcp) structure, but the multilayer structure varied. To identify the multilayer structures, transmission electron microscopy (TEM) images were compared with phase contrast image simulations. The results showed that Fe could be grown as both hcp and face-centered cubic (fcc), or fcc-like, structures. The results of image analysis of the FePt arrays were consistent with fcc structures.