Shape effects of nanocrystal catalysts in different reactions have attracted remarkable attention. In the present work, three types of α-Fe O oxides with different micromorphologies were rationally synthesized via a facile solvothermal method and adopted in deep oxidation of ethane. The physicochemical properties of prepared materials were characterized by XRD, N sorption, FE-SEM, HR-TEM, FTIR, in situ DRIFTS, XPS, Mössbauer spectroscopy, in situ Raman, electron energy loss spectroscopy, and H -TPR. Moreover, the formation energy of oxygen vacancy and surface electronic structure on various crystal faces of α-Fe O were explored by DFT calculations. It is shown that nanosphere-like α-Fe O exhibits much higher ethane destruction activity and reaction stability than nanocube-like α-Fe O and nanorod-like α-Fe O due to larger amounts of oxygen vacancies and lattice defects, which greatly enhance the concentration of reactive oxygen species, oxygen transfer speed, and material redox property. In addition to this, DFT results reveal that nanosphere-like α-Fe O has the lowest formation energy of oxygen vacancy on the (110) facet ( E (110) = 1.97 eV) and the strongest adsorption energy for ethane (-0.26 eV) and O (-1.58 eV), which can accelerate the ethane oxidation process. This study has deepened the understanding of the face-dependent activities of α-Fe O in alkane destruction.