A chemiluminescence sensor is proposed based on the dielectric coated silver hollow fiber. A ray optics model is established for the multi-layer hollow fiber to analyze the loss spectrum and chemiluminescent characteristics. And parameters such as film surface roughness and thickness are taken into consideration. The fabrication techniques for coating sol-gel sensing film inside the hollow fiber are developed. A sensing system is designed and established for detecting hydrogen peroxide concentration and a high sensitivity (22.8 nW/(mmol·L-1)) and good detection limit (3μmol/L) are achieved. This sensor has a good performance in 200 hours. It has potential applications in environmental monitoring and biological analysis fields for its simple operation, fast response, and miniaturization.