The photochemical properties of dissolved organic matter (DOM) have been of interest to scientists and engineers since the 1970s. Upon light absorption, chromophoric DOM (CDOM) can sensitize the formation of different short-lived reactive intermediates (RIs), including hydroxyl radical (OH), singlet oxygen (O) and superoxide radical anion (O). In addition, a fraction of the excited singlet states in CDOM decays into excited triplet states (CDOM*), which are also important photochemical transients in environmental systems. These RIs have a significant impact on different processes in sunlit waters, including degradation of organic contaminants and the inactivation of pathogens. Due to their transient nature and low steady-state concentrations, the use of common analytical techniques for the direct measurement of these species is impractical. Therefore, specific probe compounds (PCs) are used. PCs include furfuryl alcohol for O, and terephthalic acid for OH. In this publication, we present a critical review of the use of PCs for the assessment of the formation of photochemically generated RIs. We first introduce the concept of a PC, including the kinetic treatment and necessary assumptions needed to conduct a specific measurement. Afterward, we present short overviews of the most studied RIs and review relevant issues regarding the use of specific PCs for their measurement. We finalize by offering recommendations regarding the use of PCs in environmental photochemistry.