Adsorbed electron-rich phenyl rings, e.g., of biphenyl, may interact with the deficient rings of PCB 77 leading to better magnetic extraction. PAC3Imi+@SPIONs extracted the smallest sum of contaminant molecules overall, but show a higher preference for PCB 77 despite it being the least water-soluble as mentioned before, which should lead to highest preference for adsorption onto hydrophobic surfaces instead. This confirms the previously identified electrostatic interaction as second major interaction force at play. The electronegative chlorine atoms are attracted by the imidazolium cations. The binary coated systems, PAC3Imi+/PAC16@SPIONs and PAC3Imi+/PAC10Ph@SPIONs, again integrate both results in one system. The overall higher extraction amounts with peak in PCB 14 observed for the hydrophobic adsorbents are maintained while incorporating the higher affinity for PCB 77 in comparison to biphenyl and PCB 2 coming from the electrostatic interaction sites provided by PAC3Imi+. Here, the electron-rich phenyl ring in PAC10Ph provides no further significant interaction motif. The preference for removing PCB 77 is of particular interest as it is coplanar, substituted in both para and two meta positions while being non-ortho-substituted representing the most toxic PCBs.