The invention discloses an advanced oxidative 
coupling device and process for treating organic 
wastewater difficult to degrade. A main device body comprises an 
ozone oxidation-multi-dimensional electro-
catalysis / microelectrolysis area, an 
ozone oxidation-microelectrolysis / Fenton area, a coagulation area and an inclined plate 
sedimentation area, wherein the 
ozone oxidation-multi-dimensional electro-
catalysis / microelectrolysis area comprises a multi-dimensional 
electrolysis / microelectrolysis area at the upper part and an ozone oxidation area at the lower part; the ozone oxidation-microelectrolysis / Fenton area comprises a microelectrolysis / Fenton area at the upper part and an ozone oxidation area at the lower part. The device combines four levels of advanced oxidation systems, and electrocatalytic oxidation, ozone oxidation, 
Fenton oxidation and a microelectrolysis reaction are mutually coupled in function, so that an 
organic matter difficult to degrade is subjected to multi-level oxidation to realize complete oxidative 
cracking; when the device is used for treating the organic 
wastewater difficult to degrade, the yield and the 
production rate of *OH are increased, the 
liquid phase transfer process is accelerated, the overall current efficiency of the device is increased, operation expenses are saved, flexible regulation and control of a process unit are realized, and the device can be used for treating various kinds of organic 
wastewater difficult to degrade.