Abstract: The nanocrystalline α-Fe2O3 was prepared successfully by the reaction of polyvinyl alcohol (PVA) with ferric nitrate in combustion synthesis, where PVA is complexing agent. The effect of material proportioning on products and the nanocrystalline α-Fe2O3 were investigated experimentally by TEM, FT-IR and XRD. The results show that the product's particle edges are smooth and in uniform particle size distribution with full reaction of combustion when the mole ratio of ferric nitrate to PVA is 1 to 0.5, and the products present red granular substances. Thus, the products got from phenanthroline at 150°C are calcined at 450°C for 2 h so as to obtain nanocrystalline α-Fe2O3. The results of XRD and IR show that the organic fractions have completely been discomposed. By TEM and XRD for particle-size, the grain size is measured in the range from 25 nm to 40 nm.