Different morphologies hematite (α-Fe2O3) nanocrystals were synthesized by hydrothermal process and subsequent calcination treatment. The crystal structure and shape of the products were confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Fenton oxidation degradation of Congo red (CR) was carried out with α-Fe2O3 nanocrystals with different morphologies to compare their catalytic performance. The result shows that CR can be degraded above 90% after 2 h by using α-Fe2O3 nanorods. In addition, degradation efficiencies of α-Fe2O3 nanocrystals with different morphologies towards CR were also investigated. It reveals that α-Fe2O3 nanorods with exposed {210} and {001} planes exhibited superior Fenton oxidation performance to that of nanoparticles. It is traceable to the higher density of Fe3+ exposed on the {210} and {001} planes of nanorods than that of other morphologies crystals. The mechanism of Fenton oxidation and kinetics analysis were extensively studied.