In this work we report the preparation of magnetic hematite hollow sub-micron spheres (α-Fe2O3) by colloidal suspensions of ferric nitrate nine-hydrate (Fe(NO3)3·9H2O) particles in citric acid solution by following the sol-gel method. After the gel formation, the samples were annealed at different temperatures in an oxidizing atmosphere. Annealing at 180°C resulted in an amorphous phase, without iron oxide formation. Annealing at 250°C resulted in coexisting phases of hematite, maghemite and magnetite, whereas at 400°C, only hematite and maghemite were found. Pure hematite hollow sub-micron spheres with porous shells were formed after annealing at 600°C. The characterization was performed by X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and scanning electron microscopy (SEM). © 2011 Springer Science+Business Media B.V.