Syndiotactic polystyrene (sPS) nanofibers with a diameter of 230-720 nm have been prepared via electrospinning of chloroform solutions. The as-spun nanofibers are characterized by an s(2/1)2 helical mesomorphic form but sorption-desorption treatments allow the obtaining of nanofibrous mats characterized by the crystalline nanoporous -form. Sorption studies of 1,2-dichloroethane (DCE) from 50 ppm aqueous solutions show that DCE sorption in the nanofibrous mats occurs principally in the crystalline cavities of the nanofibers at a fast rate but the DCE equilibrium uptake is lower than for other -form morphologies.