A smart magnetic potential-responsive ion exchange nanomaterials (MPiX), gamma-Fe2O3@nickel hexacyanoferrate (NiHCF), with three-dimensionally ordered macroporous (3DOM) structure for toxic ion separation and recovery is firstly reported. The smart nanomaterial (3DOM MPiX) is successfully synthesized by coating potential-responsive NiHCF on the surface of three-dimensionally ordered macroporous gamma-Fe2O3 with superparamagnetism. Such a 3DOM MPiX shows high ion exchange capacity, excellent selectivity and rapid ion insertion kinetics, which is attributed to the open and interconnected porous channels and the large specific surface area of 3DOM and good affinity of NiHCF toward Cs+. The Cs+ adsorbed 3DOM MPiX can be regenerated by simply switching potential of magnetic electrode in a novel electromagnetic coupling regeneration system. Surprisingly, the capacity of the 3DOM MPiX toward Cs+ is nearly invariable after 20 adsorption-regeneration cycles and a high regeneration efficiency over 98% is maintained in each cycle. Moreover, the sensitive regeneration mechanism is illuminated by electrochemical experiment as well as advanced quantum chemistry calculation. It is expected to provide a versatile strategy for developing some intelligently potential-responsive nanomaterials in the controlled ion insertion/release field and designing separation devices to promote practical applications in environmental protection and resource reuse. (C) 2017 Elsevier B.V. All rights reserved.