Four kinds of solutions were prepared by dissolving cellulose acetate in dichloromethane, formic acid, acetic acid and trifluoroacetic acid respectively, and then were electrospun into fibers. The solutions were characterized for their viscosity and conductivity using rotary viscosimeter and conductivity meter, respectively. The morphology and performance of the electrospun CA fibers were investigated by scanning electron microscopy (SEM), digital microscope and X-ray diffraction (XRD). Results showed that the important factors determining the electro-spinnability of the CA solutions were boiling point, viscosity and conductivity of the resulting solutions. 8% CA spinning solution with trifluoroacetic acid as solvent had good spinnability, and the average diameter reached 236nm; the obtained fibers were mainly amorphous, but characterized for good mechanical properties.