Electrospun nanofibers are promising candidates in the nanotechnological applications due to the advantages of the nanofibrous morphology. Therefore, many attempts were reported to modify the electrospun mats to gain more beneficial properties. In the present study, we are introducing a strategy to synthesize electrospun polymeric nanofiber mats containing spider-net binding the main nanofibers. Addition with long stirring time of a metallic salt having tendency to ionize rather than formation of sol-gel in the host polymer solution reveals to synthesize a spider-net within the electrospun nanofibers of the utilized polymer. Nylon6, polyurethane and poly(vinyl alcohol) have been utilized; NaCl, KBr, CaCl2 and H2PtCl6, have been added to the polymeric solutions. In the case of nylon6 and poly(vinyl alcohol), addition of the inorganic salts resulted in the formation of multi-layers spider-network within the electrospun nanofibers mats. The synthesized spider-nets were almost independent on the nature of the salt; the optimum salt concentration was 1.5 wt%. The metallic acid led to form trivial spider-nets within both of nylon6 and poly(vinyl alcohol) nanofibers. In a case of polyurethane, few spider-nets were formed after salt addition due to the low polarity of the utilized solvents. According to TEM analysis, the synthesized spider-net consisted of joints; the later issued from the main nanofibers at Taylor's cone zone. The spider-net improved the mechanical properties and the wetability of the nylon6 nanofiber mats, accordingly a mat having amphiphilic feature has been prepared. (C) 2009 Elsevier Ltd. All rights reserved.