Controllable nanoporous hematite (CNH, α-Fe2O3) was prepared by thermal treatment of α-FeOOH at different temperatures, and the SCR activity of the prepared α-Fe2O3 was evaluated. XRD (X-ray diffraction), HRTEM (high-resolution transmission electron microscopy), N2 adsorption-desorption, XPS (X-ray photoelectron spectroscopy), and NH3-TPD (NH3-temperature programmed desorption) were utilized to characterize the catalysts. The results indicated that after thermal treatment at less than 600°C, the α-Fe2O3 catalysts exhibited excellent NO conversion that was higher than 80% in a temperature range from 300 to 400°C. CNH400 with a relatively large surface area of 47.24 m2 g–1 and many surface hydroxyl groups did not exhibit a substantially improved SCR activity even though it exhibited the best SCR activity. Therefore, the L-H mechanism was not the main reaction route for SCR of NO by α-Fe2O3. The increasing crystallization of α-Fe2O3 decreased the SCR activity, indicating that a decrease in surface oxygen defects was important for the SCR of NO and fitting the E-R mechanism. The NH3-TPD and XPS (O1s) results confirmed this hypothesis. This study provides an approach for the design and preparation of a controllable nanoporous α-Fe2O3 catalyst for SCR of NO by NH3.