Polyhaloaromatic compounds (XAr) have been found world-wide in pesticides, pharmaceuticals, flame retardants and personal care products. Most of these compounds are persistent and widely existing in the environment because of their recalcitrant properties in the soil and water. They are potentially carcinogenic to organisms and may induce serious risks to the ecosystem. Therefore, it is important to detect and quantify these ubiquitous XAr in the environment, and to monitor their degradation kinetics during the treatment of these recalcitrant pollutants. Chemiluminescence (CL) is a kind of light emission from complicated chemical reactions, during which high-energy excited-states can be generated and energy is released. CL analysis can be used to detect and quantify the specific compounds that determine the generation of CL emission. It has been recently discovered that unprecedent CL emission could be produced during the degradation of XAr mediated by advanced oxidation processes (AOPs), and a novel, rapid and sensitive CL-based analytical method was developed to not only detect XAr, but also monitor their degradation kinetics. For this distinct CL-based analytical method on the detection and measurement of XAr, it exhibits the excellent properties of relatively simple, rapid, sensitive, without complicated pretreatment.