Iron(III) oxide nanosystems are actually the focus of an intensive attention due to their low cost, non-toxicity, ample abundance, and attractive chemico-physical properties. In this work, iron(III) oxide nanomaterials were deposited by chemical vapor deposition (CVD) under O2 atmospheres in the temperature range 500–800 °C, starting from the scarcely investigated tris(tert-butyl acetoacetato)iron(III) precursor. All nanodeposits were found to consist of the α-Fe2O3 (hematite) polymorph. Surface and in-depth analyses demonstrated the presence of high purity Fe2O3, indicating the occurrence of a clean precursor decomposition under the adopted conditions. Interestingly, the system morphology could be controlled by varying the deposition temperature and ranged from the circular assembly of ordered nanosheets, to rough vortices, up to dense deposits characterized by the copresence of nanosheets and nanocolumns. The unique surface features offer great properties for advanced applications in various technological fields, such as catalysis and photocatalysis, solid state gas sensing, and magnetic recording media.