The objective was to identify the main factors and interactions influencing the fibre diameter in the production of electrospun cellulose acetate (CA) webs. A systematic parameter study was completed for producing electrospun CA fibres that were substantially free of bead defects and the effect of different process parameters during electrospinning CA were evaluated in respect of mean fibre diameter. The experiments were planned using factorial designs. Altogether three parameters, each at three levels, were selected for this study. The results indicate that polymer concentration, voltage and flow rate interact so that the magnitude of any change in the mean fibre diameter is dependent upon the level of the other factors. Furthermore, stable electrospinning conditions for CA were confirmed using an acetone: N, N-dimethylacetamide (DMAc) (2:1) solvent system that minimised the presence of structural defects in the web and promoted uniform fibre diameters.