This work focuses on the use of statistical approach in optimizing shape-size accord of electrospun cellulose acetate (CA) mats - an apt material for biomedical and industrial applications. Modulation of three processing parameters, namely potential difference, distance between tip-to-collector and feed rate led to myriad of fiber-morphology (beaded, bead free, branched and ribbon) with diverse size-spectrum. Response surface methodology using Box-Behnken design technique indicated significant linear and quadratic influence of the chosen parameters. Fibers with minimal diameter of similar to 139 nm (with a mean coherency co-efficient of 0.5192) were predicted for 30 kV (voltage), 15 cm (tip-to-collector distance) and 2 mL/h (feed rate). Reasonable agreement existed between the predicted R-squared value (0.9565) and adjusted R-squared value (0.9824) with similar observation for the experimental and model values over the entire factor space. The developed model may serve as a base model for understanding process - parametric influence on electrospinning CA and related polymers. (C) 2012 Elsevier Ltd. All rights reserved.