In this study, polycaprolactone (PCL), polylactic acid (PLA), and PLA/PCL blend electrospun fibrous webs are prepared using chloroform based solvent systems at different concentrations. The solvents to be used with chloroform are selected in accordance with the morphological and rheological structures of the polymers. While the morphology of the produced networks is observed under a scanning electron microscope, fiber diameter measurements and pore analysis are performed with Image J Software System. Although bead-free webs could not be achieved for neat PCL samples, neat PLA samples and PCL/PLA blends result in smooth fiber surfaces with homogeneous fiber diameter distributions. The results show that the increase in PLA concentration does not cause much change in fiber diameter but induces an increase in the area of pores. Furthermore, in the PLA/PCL blend, it is determined that as the ratio of PCL in the mixture increases, the fiber diameter decreases even if there is an acceptable reduction in the average pore area. (c) 2021 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of the International Conference on Multifunctional Nanomaterials.