Advanced oxidation processes (AOPs) have known increased application to treat wastewaters containing recalcitrant compounds that are hardly degraded by conventional technologies. AOPs are characterized by the formation of strong oxidants such as hydroxyl radicals, superoxide anions, hydroperoxyl radicals and singlet oxygen, which react with the contaminant, contributing to its degradation. This paper provides an overview of the determination methods of reactive oxygen species, ROS, in the application of AOPs; the methods developed in the available literature for the detection and quantification of ROS are reviewed as a first step in the assessment and detailed description of the mechanisms involved in the oxidation reactions, focusing on the critical analysis of the main strengths and weaknesses presented by the probe molecules employed in the evaluated studies. (c) 2015 Society of Chemical Industry