Electrospun mats of biodegradable polymer/clay nanocomposites were prepared in order to investigate the qualitative and quantitative correlations between electrospinning-related parameters and the fibrous morphology of the mats. A full factorial design of experiments was used for that purpose and scanning electron microscopy was employed for dimensional characterization and determination of the chosen responses. Statistical analysis revealed that solution concentration and clay loading of nanocomposite were the most important parameters affecting the morphology of the fibrous webs. This, subsequently, allowed prediction of the domain of these two parameter settings where purely fibrous morphology can be achieved and further allowed optimization of the process in the framework of response surface methodology (RSM). The structure and thermal behaviour of the nanocomposites were also characterized before and after electrospinning using X-ray diffraction, thermogravimetric analysis and differential scanning calorimetry. A multi-analyte platform is provided by the combination of RSM results for improving the nanofibrous quality and post-spinning characterization for predicting the overall performance of the electrospun web. (C) 2011 Society of Chemical Industry