A highly sensitive method for the detection and quantitative evaluation of antimony(III) using the surface-enhanced Raman scattering (SERS) technique is demonstrated. The method is based on the analysis of SERS spectra intensity of antimony bound to phenylfluorone (Sb-PhF). Phenylfluorone is widely used as an organic reagent for the spectrophotometric determination of some heavy metals. For the SERS experiment a Sb-PhF complex was adsorbed onto the silvered porous silicon substrate. The significant degradation of the SERS signal was observed during measurements in the air. The time evolution of SERS spectra at ambient and degassed conditions was investigated to find an optimal regime for SERS measurements. The limit of Sb detection in degassed samples was determined to be near 1 ng/mL, which is one order of magnitude less than that attainable by the photometric approach. The linear range of the method to Sb(III) was found to a mass concentration range of 1-10 ng/mL. This approach permits an absolute quantity of Sb(III) to be detected at the picogram level (∼50 pg). It is remarkable that a very small sample volume (50 μL) is required for SERS analysis. Moreover this technique offers high selectivity owing to the distinctive vibrational features for the metallorganic complex and to the resonance character of Raman spectra. The proposed SERS-based detection of Sb is a fast and highly sensitive method for use in environmental and industrial waste monitoring as well as for forensic science to determine gunshot residue. We expect that the approach reported herein can be further extended to develop new detection techniques for other heavy metals.