In-situ composite of Al2O3/Fe-Al with Al2O3 fibers were prepared by partial oxidation of oxygen to Fe powder and Al power, crystal phase composition and elemental composition were analyzed by XRD, NORAN. The results indicated that, the crystal composition is determined by Aluminum content, when the content is enough, FeAl3, Al and Al2O3 will be gain, on the contrary, Fe2Al, FeAl, Fe3Al and Al2O3 will be gain; Al2O3 fibers were synthesized via VLS process, the quantity of Al2O3 fibers increased with the Al content, the whisker’s diameter was improved with increasing of sintering temperature.