In recent years, the synergistic degradation of water pollutants through advanced oxidation technology has emerged as a prominent research area due to its integration of various advanced oxidation technologies. The combined utilization of peroxymonosulfate (PMS) activation technology and photocatalysis demonstrates mild and nontoxic characteristics, enabling the degradation of water pollutants across a wide pH range. Moreover, this approach reduces the efficiency of electron hole recombination, broadens the catalyst's light response range, facilitates electron transfer of PMS, and ultimately improves its photocatalytic performance. The paper reviews the current research status of photocatalytic technology and PMS activation technology, respectively, while highlighting the advancements achieved through the integration of photocatalytic synergetic PMS activation technology for water pollutant degradation. Furthermore, this review delves into the mechanisms involving both free radicals and non‐radicals in the reaction process, and presents a promising prospect for future development in water treatment technology.