A surface-enhanced Raman spectroscopy (SERS)-active extraction column based on propanethiol modified silver dendrites was fabricated. The column, which combines the advantages of solid phase extraction and SERS, may facilitate the development of rapid analysis with high reliability and accuracy. High temporal stability (under a continuous and intensive laser radiation) and excellent repeatability (repeated extraction and elution) were also achieved using this column. As an example, the quantitative analysis of fluoranthene was accomplished in the concentration range of 0.01–100 μg mL−1 with this column. The extraction process could be accomplished in 10 s and the total time of one sample analysis including extraction, spectral acquisition, elution and intermediate process could be less than 30 s. This method can greatly simplify the sample preparation and reduce the total analysis time.