This combined study using small-angle neutron scattering (SANS), X-ray powder diffraction (XRPD), transmission electron microscopy (TEM) and adsorption isotherm techniques demonstrates radical changes in the microstructure of porous hematite (-Fe2O3) nanoparticles upon calcination in air. TEM images of the as-synthesized hematite sample show that it consists of subrounded nanoparticles [50 (8)–61 (11) nm in average minimum and maximum diameters] with an apparent porous structure of nanosized pores/ channels or cracks. SANS data confirm the presence of two characteristic sizes, one originating from the particle size and the other from the pore/void structure. Furthermore, the TEM images show that the particle sizes are nearly unaffected by calcination at 623 K, whereas their pore/void structure changes radically to an apparently pitted or spongy microstructure with cavities or/and voids. The change in microstructure also causes a reduction in the surface area as calculated by gaseous adsorption. The XRPD and SANS data show that the crystallite and SANS particle sizes are virtually unchanged by calcination at 623 K. Calcination at 973 K induces a significant alteration of the sample. The XRPD data reveal that the crystallite size increases significantly, and the SANS and adsorption isotherm studies suggest that the specific surface area decreases by a factor of 5–6. The TEM images show that the particles are sintered into larger agglomerates, but they also show that parts of the porous microstructure observed in the sample calcined at 623 K are retained in the sample calcined at 973 K.