In this paper, the electrospinning of regenerated cellulose acetate (short as CA), acetone as the solvent, was basically studied, and the electrospinning setup used was self-designed. In order to explore the present condition of electrospun cellulose acetate nanofibers, the effect of traditional processing parameters on the cellulose acetate nanofibers was paid a lot of attention to, the influence of solution concentration especially, spinning voltage, the distance from spinneret to collecting screen on the morphology and the structure of the electrospun fibers. With a scanning electron microscope, the structures of the mats and the fibers were characterized and compared to the original acetate cellulose using an infrared spectrometer. It was concluded that the optimal processing parameters in the electrospinning were 8 wt%, 18 kV and 15 cm, respectively. Comparing the inner structure of the original CA and the electrospun fibers, the number of –OH groups changed apparently, this was mainly due to the dissolution.