The synthesis and electronic properties of p-type Α-Fe 2O3 nanowires and their n-type transition in a reductive ambient with ordered oxygen vacancies were analyzed. Α-Fe 2O3 was the most stable iron oxide compound material, widely used in photoelectrodes, gas sensing, catalysts, magnetic recording, and in medical fields. SEM and image of Α-Fe2O3 nanowires synthesized on an Fe64Ni36 substrate at 450°C for 10 hours in an Ar ambient of 100 seem was done. A typical TEM image of nanowire with diameter of 18nm was analyzed. The corresponding diffraction pattern confirms the phase of Α-Fe2O3 with a [001] zone axis. The results show that p-type nature of iron oxide nanowire were mainly caused by strong surface adsorption owing to the oxygen vacancies and the large surface to volume ratio.