New polymeric materials based on syndiotactic polystyrene (s-PS) are presented. These materials are able to absorb rapidly and efficiently volatile organic compounds from water and air, also when present at very low concentrations and can be considered as the first example of polymeric molecular sieves, as they display a high sorption selectivity similar to zeolites. Moreover these new molecular sieves are hydrophobic and hence seem particularly suitable for water and moist air purification. Different aspects relative to the structure, absorption properties, and host-guest interactions of these new polymeric materials are described