A modified coaxial electrospinning process including an electrolyte solution as sheath fluid was used for preparing high quality polymer nanofibers. A series of polyacrylonitrile (PAN) nanofibers were fabricated utilizing a coaxial electrospinning containing LiCl in N, N-dimethylacetamide (DMAc) as the sheath fluid. FESEM results demonstrated that the sheath LiCl solutions have a significant influence on the quality of PAN nanofibers. Nanofibers with smaller diameters, smoother surfaces and uniform structures were successfully prepared. The diameters of nanofibers were controlled by adjusting the conductivity of the sheath fluid over a suitable range and this was determined by varying LiCl concentrations. The influence of the effect of LiCl on the formation of PAN fibers is discussed and it is concluded that coaxial electrospinning with electrolyte solutions is a convenient and facile process for achieving high quality polymer nanofibers.