Necklace-like magnetite and maghemite nanorings, composed of magnetic nanoparticles (NPs) with average size about 40 nm, have been prepared via a solvothermal process in a colloidal solution by a self-assembly process. The composition, phase, and morphology of these nanorings have been characterized by X-ray diffraction, X-ray absorption, and transmission electron microscopy. In this paper, we discuss the influence of reaction conditions on the formation of nanorings structure including the amount of PVP in starting materials, reaction time, and temperature. On the basis of experimental observation, we supposed that magnetite NPs may first assemble into chains by magnetic dipole dipole interactions. These dipolar chains, which are metastable structures relative to necklace-like nanorings. then produced the rings. So, the stability of chains may determine the yield. size, and morphologies of necklace-like nanorings.