A novel sensitive and recyclable SERS substrate which can actively concentrate chromate (Cr(VI)) in water and substantially enhance Raman signal was synthesized as uniform Fe3O4@Ag nanoparticles. The surface morphology, structure, and magnetic properties were characterized using transmission electron microscopy, atomic force microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and vibrating sample magnetometry analysis. The closely spaced Fe3O4@Ag substrate with a core-shell structure exhibited a 25 nm surface roughness. The high saturation magnetization at 48.35 emu g(-1), enabled the complete and rapid separation of the substrate from the solution. The sensitivity and reproducibility of the substrate were confirmed using a common SERS probe molecule, rhodamine 6G. SERS spectra of Cr(VI) in simulated and real contaminated water showed that the symmetric stretching vibrations of Cr-O occurred at 796 cm(-1). This SERS peak area exhibited a linear dependence (R-2 = 0.9992) on the Cr(VI) concentration between 5 and 100 mu g L-1. Coexisting anions such as sulfate, nitrate, chloride, carbonate, and humic acid could decrease the sensitivity of the SERS analysis. However, the adverse effect of the competing ions may be eliminated by proper dilution of the raw sample. This study provides a reliable method for qualitative and quantitative analysis of Cr(VI). (c) 2011 Elsevier Inc. All rights reserved.