In recent years, electrospun polymer nanofibers has attracted great attention. In this study, chitosan (CS)/ poly(ethylene oxide) (PEO) nanofibers were fabricated by an electrospining method. The electrospun parameters were sdudied including ratio of CS/PEO, CS concentration, molecular weights of PEO, feeding rate. Results show that the ratio of CS/PEO and molecular weight of PEO were key factors for obtaining uniform nanofibers. SEM, IR, and XRD were used to characterize the CS/PEO nanofibers. By-products were not produced by the electrospinning process.