Abstract: A new gas-solid reaction system for singlet oxygen generation in which sodium peroxide reacted with gaseous chlorine(Na2O2/Cl2) in a fixed-bed reactor was reported. The singlet oxygen emission spectra from Na2O2/Cl2 reaction system were recorded by a near-IR sensitive Optical Multichannel Analyzer(OMA-V) and a visible sensitive CCD Optical Spectroscopy Analyzer(OPA). The 1 270 nm optical signal and the temperature of reaction zone and detection zone of the Na2O2/Cl2 reaction systems were monitored by a Ge-detector and a data-collection system, respectively. The experimental results showed that singlet oxygen was produced in the Na2O2/Cl2 reaction system, but the process was accompanied with a drastically strong heat release.