Ultrasmall spherical magnetite nanoparticles (Fe3O4 NPs) coated with one single carbon layer (Fe3O4@1C NPs) were directly synthesized by a simple, fast one-step hydrothermal reaction at low temperature (200 degrees C). The assynthesized Fe3O4@1C NPs were easily separated and purified from the resultant mixture, without the need for any additional energy input and chemicals. The as-purified Fe3O4@1C NPs not only displayed typical superparamagnetic behavior but also exhibited quite good long-term stability after being exposed to the open air under the room conditions for more than 2 months. Importantly, the long-term stored Fe3O4@1C NPs exhibited a highly sensitive surface-enhanced Raman spectroscopy (SERS) response toward Rhodamine-B (RdB) molecules with low concentration. The multifunctional and recyclable Fe3O4@1C NPs presented a prospective application for the selective enrichment and sensitive SERS detection of chemical and biomolecular assays.