Abstract: —The preparation and comprehensive structural analysis of nanostructured Nd16Fe76B8, alloy, synthesized chemically using nanodispersed Nd2O3, α-Fe2O3, and Fe3BO6 precursors, are described. The morphology and dispersion of the initial nanoparticles and the final product were studied using transmission electron microscopy. The phase composition and crystal structure were determined by X-ray diffraction, followed by refinement using the Rietveld method. The main phase of the alloy was shown to be tetragonal Nd2Fe14B, which is consistent with the results of X-ray diffraction analysis. The local state of iron was further studied by Mössbauer spectroscopy at 293 K: the spectrum is satisfactorily described by six Zeeman sextets corresponding to the positions of Fe atoms 16k1, 16k2, 8j1, 8j2, 4e, and 4c in the Nd2Fe14B structure. The hyperfine interaction parameters confirm that Fe belongs to the Nd2Fe14B phase and do not require the introduction of components characteristic of Fe2B/FeB borides. The obtained results demonstrate applicability of the chemically assisted reduction–diffusion approach for the production of nanostructured Nd–Fe–B alloys with a controlled phase structure.