Assembled heterostructure systems, as emerging functional materials, have broad applications ranging from enzyme and drug payload to catalysis and purification. However, these require trial- and -error design process and complex experimental environment to generate heterostructure materials. Here, this study describes an easy-to-execute strategy to fabricate magnetic heterostructure as multifunctional delivery system. We utilize first-row transition metal copper and nitroso/amino ligand as modules to assemble around Fe3 O4 magnetic nanoparticles by excessed mild stimuli and fabricate the magnetic heterostructure materials (Fe3 O4 @ TACN NPs (tetraamminecopper (II) nitrate)). Notably, the Fe3 O4 @ TACN NPs present with cat's-whisker structure containing ligand and metal center. The nitroso-group ligands exhibit strong binding affinity to heme-structure enzyme, ensuring effective capture and isolate of cytochrome C (Cyt-c), resulting in their excellent isolation property. The copper complex-powered magnetic heterostructure materials can effectively isolation Cyt-c from complex biological sample (pork heart). Importantly, the Fe3 O4 @ TACN NPs coordinated with heme-structure, induced methionine 80 (Met80) disassociates from heme prosthetic group, and contributed to peroxidase-like (POD-like) activities increasing. These results exhibit that copper complex-powered magnetic heterostructure materials can not only satisfy the Cyt-c isolation and immobilization in an alkaline medium, but also be of the potential for improving the immobilization enzyme reactor performance.