The present paper focuses on the development of narrow-band thin-layer chromatography (TLC) coupled with Fourier transform Infrared spectroscopy (FTIR) technique. We adopted a new method to prepare a narrow-band TLC plate by using silver iodide as stationary phase. The narrow-band TLC plate exhibits a variety of advantages: the preparation time is about 20 minutes, while 3–7 days are needed to prepare a common TLC plate suitable for TLC/FTIR analysis by using “settlement volatilization method”. Furthermore, the usage of stationary phase in narrow-band TLC plates decreases by about one order of magnitude in comparison with that of common TLC plates. This is very important for an expensive stationary phase such as silver iodide. In addition, experimental results of TLC/FTIR analysis on mixed samples containing rhodamine B and bromocresol green demonstrate the detection limit significantly improves by using the narrow-band TLC technique.