Since the Industrial Revolution, persistent organic compounds (POPs) in wastewater have been at the heart of water pollution control due to their complexity, stability, and high toxicity. Despite the rapid development of water treatment methods, there is no single method that can stand out from the crowd:advanced oxidation technology has significant advantages in the treatment of POPs, but it has the limitations of high cost, non-selective attack, and easy quenching and inactivation of active species; biological treatment is universal and has good impact resistance, but it has limitations in the treatment of difficult-to-degrade pollutants. Intimately coupled advanced oxidation and biodegradation (ICAB) technology organically combines the advantages of advanced oxidation and biodegradation, solves the limitation of their individual action, and has been proved to be effective in degrading many organic substances such as mineralized chlorophenols, antibiotics, dyestuffs, nitrobenzene, polycyclic aromatic hydrocarbons and so on. This paper reviews the concept and features, core components, advantages and current applications of the intimately coupled advanced oxidation and biodegradation technology, as well as its bottlenecks in terms of efficient quenching of carrier materials, active species quenching and high mass transfer reactor design, and looks forward to the future development of its application in practical water treatment. The aim of the paper is to promote the application and development of new ICAB technology in the field of treatment of non-degradable organic wastewater.