Comprehension of selective recognition of anions is confined to a phenomenological list of solvents, hardly surpassing Pedersen’s empirical observations of cationic-crown ether binding. In this work, a novel strategy employing thin-layer oil membrane extraction (TOMX) on the surface of concentrated hydrochloric acid is proposed for controllable recognition and separation of anions with different hydration configurations. Four typical chloric-complexing anions, RhCl63−, PdCl42−, PtCl62− and FeCl4−, usually coexisting in the concentrated hydrochloric acid leaching solutions of precious metal concentrates were focused. A surprising phenomenon was noticed that the octahedral RhCl5(H2O)2− anions with inner-coordinated water molecules were preferentially recognized by 18C6 macrocyclic molecule. However, the planar quadrilateral Pd (II) chloric-complexing anions with a hydration configuration via water molecules attacking the central Pd (II) atoms along the Z-axis direction can be separated subsequently. The Pt (IV) and Fe (III) chloric-complexing anions respectively with an octahedral and tetrahedral outer-coordinated hydration shell configuration were the last to be recognized. Such an order in extracting Rh (III) > Pd (II) > Pt (IV) > Fe (III) anions depends on their hydration capacity and the preferential affinity towards the interface, which is almost impossible during the conventional stirring and oil droplet dispersed extraction. Because of a lower concentration of dissociated hydrogen ions on the surface of concentrated hydrochloric acid compared to its bulk concentrations, the hydration of those chloric-complexing anions was enhanced. The Rh (III) anions with inner-coordinated water molecules exhibit a higher interfacial affinity than other anions. The water molecules entering the inner coordination layer of Rh (III) chloric-complexing anions, cooperating with its outer-coordinated hydration shell, act as a hydrogen bond “water bridge” to interact with 18C6 molecules, which makes it easier to feel the influence from the aqueous laminar shear flow under the thin-layer oil membrane, thereby driving the preferential recognition of easily hydrated Rh (III) anions at the interface. The controllable “water bridge” interactions driven by shear flow can be activated or deactivated on the surface of concentrated hydrochloric acid by adjusting the shear flow rate. This work lays a foundation for the future development of a controllable flexible molecular recognition technology at liquid–liquid interfaces.