PVA(Polyvinyl alcohol)/chromium nitrate/aluminum nitrate composite nanofibers were prepared by using sol-gel processing and electrospinning technique. By high temperature calcinating the above precursor fibers, Cr2O3/Al2O3 composite nanofibers were successfully obtained. The fibers were characterized by XRD, IR, and SEM, respectively. The results showed that the crystalline phase and the morphology of the fibers depended on the calcination temperatures.