Increasing evidence has shown that plastic pollution and water contamination are serious environmental issues. Herein, by utilizing cheap, abundant waste expanded polystyrene (EPS) as the raw material, high-value-added porous organic polymers (POPs) were prepared through a Friedel-Crafts alkylation reaction using two types of cross-linkers and applied to the removal of antibiotics and chlorophenols. The structural characterization indicated that the pore structure of the two types of POPs (EPS-FDA and EPS-CC) can be successfully tuned by stepwise crosslinking with dimethyl acetal (FDA) and introducing different doses of cyanuric chloride (CC) as a cross-linker. Notably, EPS-FDA and EPS-CC have high specific surface areas with abundant micro/mesoporous structures. The maximum adsorption capacity of EPS-FDA-2 for TC removal (calculated by the Langmuir model) can reach 621.12 mg.g(-1), and the amount of 2,4-DCP on EPS-CC-3 is up to 680.27 mg.g(-1). Moreover, possible adsorption mechanisms including pore filling and pi-pi electron interactions are discussed. Hydrogen bonding also plays a role in the removal process of 2,4-DCP by EPS-CC-3. This study developed a novel and green synthetic method for the efficient recycling of waste plastics and demonstrated an industrialized approach for conversion of waste plastics into high-value-added adsorbing material, which could be a promising candidate for the removal of organic contaminants.