A novel architectures consisting of plum-like Fe3O4 microspheres strung together by nitrogen-doped carbon nanotubes (CNxNTs) was prepared by in situ growth strategy in liquid ethylene glycol (EG). The structure and morphology of the as-prepared samples were characterized by XRD, SEM, and EDS. Results indicated that plum-like Fe3O4 microspheres with the size of about 200–300nm were uniformly self-assembled along the surface of the CNxNTs to form necklace-like structures. The magnetic saturation value was about 61emu/g for the Fe3O4/CNxNTs architectures, which is enough strong to preserve its good performance of magnetic recovery. The novel magnetic hybrid materials are believed to have potential applications in sensors, separation technology, microwave absorption, nanotechnology, and biomedical areas.