These results indicate an interplay of hydrophobic effect driven segregation (i.e., hydrophobic segregation) and electrostatic interaction as the two major non-covalent interaction motifs between the investigated pollutants and the functionalized adsorbent surface. PCBs are less water soluble with increasing chlorination degree. For biphenyl, PCB 2 and PCB 14 a respective increase in removal amounts is seen for all adsorbent systems corresponding to their decreasing water solubility. This in combination with the performance of PAC16@SPIONs and PAC10Ph@SPIONs supports a strong hydrophobic segregation on the nanoparticle surface for these pollutants. These adsorbents, however, lose a lot of performance for PCB 77 despite it being least water-soluble. Here, PAC3Imi+@SPIONs works best. This may be due to the positive charges on the surface that can attract electron-rich chlorine atoms, of which PCB 77 comprises the most among the investigated molecules. Aqueous solutions of 7 mL initially contained 7 nmol (1 µM) of pollutant at neutral pH and were treated with 5.0 ± 0.1 mg of SPIONs. Hydrophobic PAC16@SPIONs and PAC10Ph@SPIONs remove biphenyl, PCB 2 and PCB 14 more efficiently with a trending increase for less water solubility, while PAC3Imi+@SPIONs drastically outperforms them for PCB 77 despite it being least water-soluble. Binary SAMs on SPIONs show performances in between the extrema. Data are represented as mean ± standard deviation.