Hierarchically nanostructured hydroxyapatite (HA) hollow spheres assembled from nanorods have been successfully synthesized using CaCl2, NaH2PO4, and potassium sodium tartrate via a solvothermal method at 200 °C for 24 h in water/N,N‐dimethylformamide (DMF) mixed solvents. The ratio of water to DMF plays a key role in the formation of hierarchically nanostructured HA hollow spheres. The potassium sodium tartrate was used as a chelating ligand and a template molecule in the synthesis and self‐assembly of HA nanorods. The products were characterized by X‐ray powder diffraction, and field‐emission scanning electron microscopy (FESEM), transmission electron microscopy, high‐resolution transmission electron microscopy (HRTEM), energy‐dispersive X‐ray spectra (EDS), Brunauer–Emmett–Teller (BET), and Fourier transform infrared spectrometry. FESEM and TEM images indicated that hollow spheres of about 3.6 μm in diameter were built by HA nanorods. On the basis of experimental results, a possible formation mechanism of these hierarchically nanostructured HA hollow spheres in the growth processes was proposed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)