Cellulose acetate (CA) membranes and films were fabricated, respectively, by electrospinning and solvent casting. A systematic analysis of structure and properties was made to compare the differences between nanotexture and casting texture. Scanning electron microscopy, X-ray diffraction and thermal analysis were used to characterize the morphology, inner structure and thermal behavior of electrospun CA membrane, casted CA film as well as original CA powder. In addition, the pore size distribution and surface hydrophilicity of electrospun membrane and casted film were tested. It was found that the nanotexture produced by electrospinning process had a significant effect on the structure and properties of CA materials. The pore size distribution of electrospun membrane was more uniform, although the mean pore size was larger. In addition, the electrospun CA membrane possessed higher crystallinity and better thermal stability, compared with casted CA film. The results also showed that the electrospun membrane gave a contact angle of 127.2 degrees and was observably more hydrophobic than the casted film, reporting a contact angle of approximately 74.4 degrees.