The reaction of gold nanoparticles with a potassium periodate-sodium hydroxide-carbonate system undergoes chemiluminescence with three emission bands at 380-390, 430-450, and 490-500 nm, respectively. It was found that the light intensity increased linearly with the concentration of the gold nanoparticles, and the CL intensity increased dramatically when the citrate ions on the nanoparticle surface were replaced by SCN(-). The shape, size, and oxidation state of gold nanoparticles after the chemiluminescent reaction were characterized by UV-visible absorption spectrometry, transmission electron microscopy (TEM), and X-ray photoelectron spectrometry (XPS). Gold nanoparticles are supposed to function as a nanosized platform for the observed chemiluminescent reactions. A chemiluminescent mechanism has been proposed in which the interaction between free CO(3)(*-) and O(2)(*-) radicals generated by a KIO(4)-NaOH-Na(2)CO(3) system and gold nanoparticles results in the formation of emissive intermediate gold(I) complexes, carbon dioxide dimers, and singlet oxygen molecular pairs on the surface of the gold nanoparticles. This work is not only of great importance for gaining a better understanding of the unique optical and surface properties and chemical reactivity of nanoparticles but also of great potential for developing new biosensing and immunolabeling technologies.