α-Fe2O3 mesocrystals and nanorings have been prepared by hydrothermal method, using phosphate and sulfate ions as additives. Hydrothermal treated at 180 °C for 24 h in presence of C3H8NO6P and Na2SO4 leads to the formation of capsule-shaped α-Fe2O3 mesocrystals, when the reaction time prolonged to 96 h α-Fe2O3 nanorings formed. It can tune the size and morphology of the final products by varying the ratios of phosphate and sulfate ions to ferric ions. XRD, SEM, TEM, HRTEM, UV-Vis, FT-IR were used to characterize the products. A formation process involving the selective adsorption and the cooperative coordination effect have been deduced.