Non-woven structures of cellulose acetate (CA) fibres of 90 nm-5 mu m in diameter (spinning parameters 90 nm beaded fibres: 12% CA in EtOH-DMSO 1/1, 22 kV, 30 cm, 0.5 mL/h; maximum 5 mu m diameter fused fibres spun with 14% CA in Ac-BenzOH 2/1, 22 kV, 24 cm, 13 mL/h) were produced by electrospinning. On the basis of Hansen solubility theory, composition of binary solvent mixtures (ketones-acetone, methyl ethyl ketone (MEK), and alcohols-benzyl alcohol, propylene glycol and dimethylsulphoxide) was optimized with respect to control of fibre felt morphology. Fibre networks of high packing density were obtained with binary low-volatile alcohols/MEK solvent mixtures, a decreased spinning distance and an increased feed rate. Substituting MEK by acetone in the solvent mixture resulted in the formation of nanofibre felt with a low degree of fibre cross-links. Thus, solvent control is a key aspect for control of electrospun fibre felt structures, which may serve as scaffolds for tissue engineering.