According to the chemiluminescence reaction mechanism of nitric oxide (NO) and ozone (O₃), a new cylindrical total reflection S-type optical cavity design for rapid detection of NO gas is proposed. The optical cavity model is based on the total reflection S-type structure on the inner wall of the cylinder. Optical software ZEMAX was used to simulate the optical path of the model, and software FLUENT was used to simulate and verify the structure. The comparative analysis showed that the chemiluminescence collection efficiency of the S-type optical cavity collection path was 36.6%, and the gas reaction and mixing in the S-type optical cavity model was more sufficient, and the reaction mixing stability error was 0.049, which was 2 times higher than the traditional stability error. The model is simple in structure and meets the new national standards. It provides a practical idea of design for the real-time exhaust gas detection.