The search for a simple and clean approach toward the production of sulfate radicals for water treatment gave rise to electrochemical and photoelectrochemical activation techniques. The photoelectrochemical activation method does not just distinguish itself as a promising activation method, it is also used as an efficient water treatment method with the ability to treat a myriad of pollutants due to the complementary effects of highly reactive oxidizing species. This perspective highlights some merits that distinguish sulfate monoanion radicals from hydroxyl radicals. It highlights the electrochemical, photoelectrochemical, and in situ photoelectrochemical routes of generating sulfate radicals for advanced oxidation process approach to water treatment. We provide a detailed account of the few known applications of sulfate radical enhanced photoelectrochemical treatments of water laden with organics. Finally, we placed this area of research in perspective by providing outlooks and conclusive remarks.