A fluorescence switch based on photoisomerization of naphthopyran (NP) has been designed by employing 2-(pyridin-2-yl)-benzimidazole (BPI) and the naphthopyran containing two pyran rings (NP) as fluorescent dye and photochromic compound, respectively. The fluorescence switch of benzimidazole derivative can be modulated either by controlling the irradiation time of UV light or by adjusting the amount ratio of fluorescent benzimidazole derivative to photochromic naphthopyran in both solution and polymethyl methacrylate (PMMA) film. The experimental results indicated that the decrease of fluorescence intensity of benzimidazole derivative is attributed to the interaction of benzimidazole with naphthopyran.