The paper reports a green synthetic route for nanosized hematite colloids with an excellent monodispersity, using green vitriol and ammonia as raw materials. The reaction conditions of the synthetic route were studied and the as-prepared samples were characterized by XRD, TEM, TG-DTA, DLS, and XPS. The results indicated that the key factors for the monodispersity of the colloidal product were preheating reactants and washing repeatedly the intermediate Fe(OH)3. When the initial pH was set as 4 or 5, the transformation product of Fe(OH)3 was the pure α-Fe2O3 with the minim adsorptive sulfate ions. Contrarily, the mixtures of α-Fe2O3 and α-FeOOH were obtained at the pH 6 or 7, which were related to the mechanism of transformation reaction. In addition, the concentration of Fe(OH)3 should be less than or equal to 0.2 mol/L in order to prepare the qualified nanosized hematite colloids. The researches proved that the excellent monodispersity of the colloidal product resulted from a fine dispersion state of the synthetic system during the whole process and that it was a significant way to obtain the nanosized metallic oxide colloids from the corresponding metal hydroxide due to avoidance of hyperspeed centrifugal separation or dialysis operation.