Humic acids (HA) are the most important photosensitizers in the ocean and generate highly reactive oxygen species (ROS), known as photochemically produce reactive intermediates (PPRI), which degrade organic pollutants. Thus, to reveal the fate of organic pollutants in an aqueous environment, it is important to understand the natural photodegradation phenomenon caused by HA. Three ROS generated from HA, O-1(2), O2- and (OH)-O-center dot, were measured using different probe compounds and instrumental techniques. In this study, HBCD (hexabromocyclododecane), a newly listed one of persistent organic pollutants (POPs) under the Stockholm Convention, was studied to understand the phototransformation mechanism, which has not been sufficiently investigated in terms of its environmental fate and transport, despite the distinctive features of its diastereoisomers. The results showed that the diastereoisomer-specific distributions of alpha-, beta-, and gamma-HBCD were related to the acceleration and retardation of photodegradation in the presence of AHA (Aldrich Humic Acid) under simulated solar light, and only alpha-HBCD was rapidly photodegraded as the amount of AHA increased relative to the absence of AHA. This study provides the first characterization of the behavior of photosensitized HBCD degradation in aquatic systems.