The purpose was to interpret the varying morphology of electrospun cellulose acetate (CA) fibres produced from single and binary solvent systems based on solubility parameters to identify processing conditions for the production of defect-free CA fibrous webs by electrospinning. The Hildebrand solubility parameter () and the radius of the sphere in the Hansen space () of acetone, acetic acid, water, N,N-dimethylacetamide (DMAc), methanol, and chloroform were examined and discussed for the electrospinning of CA. The Hildebrand solubility parameter () of acetone and DMAc were found to be within an appropriate range for the dissolution of CA. The suitability of the binary solvent system of acetone: DMAc (2 : 1) for the continuous electrospinning of defect-free CA fibres was confirmed. Electrospun webs exhibited improved tensile strength and modulus after heat and alkali treatment (deacetylation) of the as-spun material, and no major fibre morphological degradation occurred during the deacetylation process.