Trichloroethylene (TCE) and tetrachloroethylene (PCE) are chlorinated organic liquids widely employed in various industrial processes. However, due to their high toxicity and cancerogenic proprieties, these compounds are recognized as environmental pollutants. Therefore, the removal of TCE and PCE from wastewater is a crucial objective for environmental protection. This work investigated the adsorption capacity of syndiotactic polystyrene (sPS) fibers, activated in the nanoporous crystalline δ form, to remove volatile organic compounds from aqueous solutions. TCE can be adsorbed in the nanoporous crystalline δ form of sPS, leading to the formation of a clathrate structure, in which it acts as the guest molecule. This adsorption mechanism allows for high process selectivity, as well as the capture of even trace amounts (in the ppb range) of the pollutants under consideration, in relatively short times (e.g., 67 hours). Also, a process with two successive adsorption tests was performed replacing the solid used for the first contact with the contaminated solution with fresh δ-sPS fibers. This approach allowed the reduction of TCE concentration down to 8 ppb. In conclusion, δ-sPS nanoporous fibers demonstrated a great potential for the efficient removal of chlorinated organic compounds from wastewater, providing a promising alternative to conventional adsorption processes.