Nearly monodisperse iron oxide colloidal nanocrystals prepared by nonhydrolytic high-temperature solution method were obtained with two different sizes and degrees of oxidation. The characterization of the structural features of the nanocrystals was performed by a multitechnique approach including transmission electron microscopy, X-ray diffraction and X-ray absorption spectroscopy, energy filtered electron microscopy imaging, and SQUID magnetometry. The different techniques provided complementary information on the local oxidation state of iron in the iron oxide nanoparticles, the stability of the phases, the exact crystal structure, and the compositional homogeneity. X-ray diffraction, transmission electron microscopy, and extended X-ray absorption spectroscopy show that the addition of oxidizer to the iron precursor gives rise to monodisperse polycrystalline nanoparticles made out of FeO plus a spinel phase. X-ray absorption near-edge structure, which is very sensitive to the oxidation state and local environment of iron in the different iron oxides, was used to distinguish among isostructural spinel phases of iron (II, III) oxide (magnetite) and iron(III) oxide (maghemite). Singlecrystalline spinel nanoparticles are obtained upon sequential oxidation: in smaller nanoparticles a mixture of mainly Fe3O4 and γ-Fe2O 3 is present, whereas the larger nanoparticles are made out of γ-Fe2O3, as also supported by SQUID magnetization measurements. The importance of a multitechnique approach for the elucidation of the compositional and structural details in addition to geometrical parameters in the characterization of nanocrystalline iron oxides is pointed out. © 2009 American Chemical Society.