A detailed study of the composition and structure of Co-doped maghemite nanoparticles with systematically varying composition has been carried out by transmission electron microscopy (TEM) techniques, such as high-resolution TEM, scanning TEM, and energy-dispersive X-ray spectrometry, and by X-ray absorption spectroscopy at the Fe and Co K-edges, analyzing both the extended X-ray absorption fine structure and the X-ray absorption near-edge structure regions. The latter techniques, in particular, allow us to determine the degree of inversion of divalent and trivalent metal ions among the octahedral and tetrahedral sites in the spinel structure of the nanoparticles and give detailed information on atomic distances. The samples consist of single-crystal nanoparticles with a composition corresponding to the Fe/Co ratio used in the synthesis. The degree of inversion is quite similar for all samples and close to the value found in a pure cobalt ferrite bulk sample. © 2013 American Chemical Society.