Photochemical reactions widely occur in the aquatic environment and play fundamental roles in aquatic ecosystems. In particular, solar-induced photodegradation is efficient for many organic micropollutants (OMPs), especially those that cannot undergo hydrolysis or biodegradation, and thus can mitigate chemical pollution. Recent reports indicate that photodegradation may play a more important role than biodegradation in many OMP transformations in the aquatic environment. Photodegradation can be influenced by the water matrix such as pH, inorganic ions, and dissolved organic matter (DOM). The effect of the water matrix such as DOM on photodegradation is complex, and new insights concerning the disparate effects of DOM have recently been reported. In addition, the photodegradation process is also influenced by physical factors such as latitude, water depth, and temporal variations in sunlight as these factors determine the light conditions. However, it remains challenging to gain an overview of the importance of photodegradation in the aquatic environment because the reactions involved are diverse and complex. Therefore, this review provides a concise summary of the importance of photodegradation and the major processes related to the photodegradation of OMPs, with particular attention given to recent progress on the major reactions of DOM. In addition, major knowledge gaps in this field of environmental photochemistry are highlighted.