Since the water solubility of PCBs decreases with increasing degree of chlorination, an increasing segregation from biphenyl to PCB 14 onto PAC16@SPIONs and PAC10Ph@SPIONs is observed. Counterintuitively, this inverts for the least water-soluble PCB 77, which is removed best by PAC3Imi+@SPIONs. This is attributed to electrostatic interactions between the cationic imidazolium and electronegative chlorine atoms. The orthogonal properties of these SAMs can be integrated into single adsorbent systems with binary SAMs comprising PAC3Imi+ and PAC16 or PAC10Ph on one surface. These systems show magnetic extraction performances in between the extrema, while being dominated by the influence of the uncharged molecules. Since PCBs usually occur in mixtures, the pollutants were also removed in competition. Here, the described trends continue with PAC3Imi+@SPIONs showing highest affinity to PCB 77, while the hydrophobic adsorbents extract PCB 14 best. A convolution of both behaviors is found for the binary SAM-coated systems providing highest removal amounts for PCB 14, while having preference for PCB 77 over biphenyl and PCB 2, which is of particular interest as PCB 77 is among the most toxic PCBs. With PAC3Imi+/PAC10Ph@SPIONs as surrogate, it was shown that magnetic extraction of PCB mixtures works just as well in a natural water matrix, i.e., river water collected from the Regnitz in Erlangen, Germany. By employing more SPIONs higher removal efficiencies can be achieved approaching up to 97.6 ± 0.9 % removal in a single treatment as demonstrated for PCB 14. Furthermore, recyclability of these adsorbents was shown. The binary SAM does not degrade over three cycles of application. Ultimately, we believe that the demonstrated approach of magnetic water cleaning of PCBs is very promising as efficiently removing POPs at low concentrations from water remains a challenge. Being able to address individual components of pollutant molecule mixtures preferentially by tailoring the molecular shell on large surface area providing nanoadsorbents may be beneficial in the future considering the majority of pollutants is still out there.