A novel facile method for the detection of the phosphodiesterase type 5 enzyme inhibitors added illegally into health products was established using thin-layer chromatography and surface enhanced Raman spectroscopy combined with BP neural network. When the detection conditions were optimized in detail, a repetitive adding procedure of silver colloids with the total amount keeping constant was used to improve the enhancement effect of surface enhanced Raman spectroscopy. According to the main Raman peaks and the retention factor of analyte, the data predictive model was established. Under the optimized experimental conditions, this method was successful to apply to detect the artificially produced model samples, and the limit of detection less than 5 mg/kg was obtained. Based on the excellent sensitivity of this method, the real samples have been detected accurately and the detection results were confirmed by high-performance liquid chromatography. In addition, the developed method was suitable for the detection of other adulterants, especially those that have similar chromatographic or spectroscopic behaviors.