AbstractThe chemiluminescence behaviour and mechanism of peroxynitrous acid and Ru(bpy)32+ were studied in the presence of short-chain alcohols (methanol, ethanol, propan-1-ol, propan-2-ol, butanol, 2-methylpropan-1-ol, pentanol). It was found that the chemiluminescence intensity of peroxynitrous acid and Ru(bpy)32+ system could be significantly enhanced by these seven short-chain alcohols. The maximum chemiluminescence wavelength of 608 nm of [Ru(bpy)32+]* in the excited state was attributed to the reaction between Ru(bpy)32+ and dihydroxyalkyl radicals which were generated during the redox course of peroxynitrous acid and alcohols. In addition, the chemiluminescence signals of the system presented depended largely on the solubility and branched-chain structure as well as the length of carbon chain. The analytical characteristics and parameters of the peroxynitrous acid/Ru(bpy)32+/alcohols chemiluminescence system were investigated under optimum conditions.