We report herein a novel chemiluminescence (CL) phenomenon triggered by light irradiation when a fluorescent dye, for example hematoporphyrin, fluorescein, eosin, or methylene blue is present in the luminol solution. A possible mechanism is proposed for the photoinduced chemiluminescence (PICL) reaction. Compared with reported methods for CL triggering, for example flow-injection, static reagent injection, and the electrochemical technique, the proposed in-situ PICL method presented has three advantages. First, the method is more selective, because the PICL signal of the target fluorescent dyes is initiated by excitation at a selective wavelength only. Second, the space and time resolution of the PICL method are better. Last, and most important, compared with injecting a reagent or inserting a electrode into the CL system to initiate the CL reaction, with the in-situ PICL method there is no physical interference with the target detecting system. All these advantages of the PICL method indicate it has many potential applications in the analytical sciences. The proposed method was applied to analysis of urine containing adrenaline. The linear range for adrenaline is 2.0 × 10−10–1.0 × 10−7 g mL−1 and the detection limit is 6.0 × 10−11 g mL−1.