Emerging contaminants (ECs) are characterized by stable structures and low concentrations, making them difficult to remove completely using traditional wastewater treatment processes. ECs are posing potential risks to aquatic ecosystems and human health. Advanced oxidation processes (AOPs) can rapidly and effectively degrade persistent pollutants. However, for trace refractory ECs in real water matrices, AOPs require excessive oxidants or consume more energy, resulting in low cost-effectiveness of water treatment and even secondary pollution. Therefore, developing efficient and low-energy selective oxidation processes for treating trace ECs in water has practical significance. Targeted adsorption-transformation technology can effectively enhance the utilization of free radicals and efficiently remove trace ECs. The concept of advanced water purification processes is elaborated based on selective oxidation, with a focus on the technical characteristics and recent development of selective electrochemical adsorption-transformation technology to remove per- and polyfluoroalkyl substances (PFAS) from water. Finally, an outlook is provided on the future research directions and trends.