Potentially toxic metal ions (Xn+: Rb+, Sr2+, Cr3+, Mn2+, Ni2+, Zn2+, Cd2+) usually coexist with uranyl (UO2+), which will have a great influence on the selective adsorption process. Here, the core-shell MFe2O4-TiO2 (M = Mn, Fe, Zn, Co, or Ni) nanoparticles were synthesized and assessed as new selective adsorbents. The results reveal that TiO2(101) preferentially grows along the MFe2O4(311)/(111) orientation. The M2+ ions as the mediators transfer the holes from MFe2O4 to TiO2, at the conduction bands. On the TiO2(101) surfaces and TiO2(101)-TiO2(101) gaps, the paired active electrons mainly complex with water molecules as hydroxyl radicals to capture Xn+ ions, forming an ion layer to block UO22+ from being adsorbed. Simultaneously, it should be noted that an interesting adsorption pathway was UO22+ being horizontally and irreversibly adsorbed in the MFe2O4(311)/(111)-TiO2(101) interface, and therein, the stable adsorption capacity was found to be 66.78 mg g(-1) in the MnFe2O4(311)/(111)-TiO2(101) interface. Finally, a mechanism of hybrid orbitals between MnFe2O4-TiO2 and UO2+-X-n(+) was proposed.