Porous nylon-6 fibers are obtained from Lewis acid-base complexation of gallium trichloride (GaCl3) and nylon-6 using electrospinning followed by GaCl3 removal. DSC and FTIR results reveal that the electrospun fibers, prior to GaCl3 removal, are amorphous with no hydrogen bonds present between nylon-6 chains. GaCl3 being a Lewis acid interacts with the Lewis base sites (C=O groups) on the nylon-6 chains, thereby preventing the chains to crystallize via intermolecular hydrogen bonding. Subsequent removal of GaCl3 from the as-spun fibers by soaking the electrospun web in water for 24 h leads to the formation of pores throughout the fibers. While the average fiber diameter remains effectively the same after salt removal, the average surface area increases by more than a factor of 6 for the regenerated fibers. The dual use of a metal salt (Lewis acid) to (a) facilitate fiber formation by temporary removal of polymer interchain interactions and (b) act as a porogen provides a facile approach to obtain porous fibers via electrospinning.