Simultaneous SAXS-WAXD measurements are carried out to gain information about the microstructure and the molecular orientation developed by polymeric chains during the electrospinning process. Three semicrystalline polymers were studied, namely polyacrylonitrile, Nylon 6,6, and poly(ethylene oxide), as non-woven mats with either randomly arranged or aligned electrospun fibers. Mat thermal and morphological properties are investigated, together with their structural details in order to derive their hierarchical structure from the macro to the nano-scale. SAXS patterns have an elliptical shape with the main axis along the equator direction. No reflections are noticeable along the meridional direction, suggesting that the investigated electrospun fibers have a fibrillar structure with no trace of lamellar morphology. Combining the values of the unit cell and of the crystal size it can be concluded that in the fibers the ordered domains are organized into a bundle of fibrils due to the lateral aggregation of roughly 10 unit cells and the regular ordering of about either 50 (Nylon 6,6 and polyacrylonitrile) or 25 (poly(ethylene oxide)) cells in the chain direction. (C) 2015 Elsevier Ltd. All rights reserved.