Nanorods and micro-octahedrons of alpha-Fe2O3 were selectively synthesized through one-step hydrothermal treatment of iron(III) chloride in aqueous formamide solution for different time. The resulting samples were characterized with XRD, FE-SEM, TEM, and FT-IR. It was found that monodispersed nanorods were 10-25 nm in diameter and 50-100 nm in length, while the octahydrons were 100-400 nm in size. These alpha-Fe2O3 nanorods and micro-octahedrons exhibited quite different catalytic performances on thermal decomposition of ammonium perchlorate. The nanorods significantly reduced the decomposition temperature of ammonium perchlorate, but the micro-octahedrons did not. This study provides alternative choice of good burning rate catalysts for composite solid propellants in solid fueled rockets. (c) 2007 Elsevier B.V. All rights reserved.