In this study, hematite α-Fe2O3 half-hexagon nanoplates have been successfully prepared by ethanol–water mediated microwave assisted solvothermal method. The high crystalline nature and rhombohedral crystal structure of the synthesized α-Fe2O3 were confirmed from X-ray diffraction (XRD) results. No impurity phase other than hematite α-Fe2O3 was detected. Raman spectroscopy results further revealed the hematite structure of α-Fe2O3. X-ray photoelectron spectroscopy (XPS) study disclosed the chemical composition and valence states in the synthesized α-Fe2O3 material. Field emission scanning electron microscope (FE-SEM) and transmission electron microscope (TEM) studies confirmed the half-hexagon plate like architecture for α-Fe2O3 along with some irregular shape nanoplates. When treated as an anode material for Li ion battery (LIB), α-Fe2O3 half-hexagon nanoplates delivered a reversible discharge capacity of 520 mAh.g−1 after 100 cycles at a high current density of 500 mA.g−1. The α-Fe2O3 half-hexagon nanoplates also exhibited excellent cycling performance and coulombic efficiency. The excellent performance of the α-Fe2O3 electrode is mainly ascribed to the plate like morphology of the particles, which offers large effective contact area with the electrolyte and significantly enhances the electrochemical performance.