A new kind of chemiluminometric sensing cell based on hollow fiber is proposed by combining sol-gel enzyme immobilization and dielectric-coated metallic hollow fiber. The fabrication techniques for coating sol-gel sensing membrane inside the hollow fiber are studied. Transmission mode and luminescence mode of the new device are simulated, and optimization of system parameters is discussed according to the calculation results. A hollow fiber based sensing system is designed and established for detecting hydrogen peroxide concentration. And it is applied to detect the hydrogen peroxide concentration in contact-lens disinfectant solution. A high sensitivity (10 μM) and good repeatability are achieved. The system has potentiality in biochemical research, environmental protection and food industry, owing to its easy operation, rapid response and miniaturization.