The invention pertains to the technical field of treatment of waste water, and particularly relates to a method of 
hydrolysis-catalytic iron-aerobic 
coupling for treating poisonous and harmful hard-degradation waste water, which comprises the following steps: waste water after 
primary treatment directly enters an up flow type 
hydrolysis system 1 and stays for 4.0-10.0 hours; the 
effluent enters an 
electrolytic cell in the catalytic iron; the 
mass ratio of iron scraps and 
copper scraps in the 
electrolytic cell of the catalytic iron is 1:1 to 20:1, the bulk 
specific weight thereof is 0.1 to 0.3, the 
contact time thereof in a filling area is 0.5 to 2.0 hours, and the 
reflux ratio of the 
effluent refluxing to the up flow type 
hydrolysis system is 20 to 100 percent; the 
effluent enters an aerobic biological 
treatment system and stays for 6.0 to 12.0 hours; then the effluent enters a 
solid-liquid 
separation system with a 
reflux ratio of 
sludge being 10 to 50 percent; and the effluent of the 
solid-liquid 
separation system refluxes to the 
electrolytic cell of the catalytic iron with the 
reflux ratio being 20 to 200 percent. Under the premise of fully playing the function of different treatment units and maintaining the 
treatment effect and respective advantages, the treatment method of waste water realizes the 
coupling synergetic action of the three units, strengthens the 
impact of the 
system to 
water quality and water quantity load, reduces a plurality of steps of pretreatment, effectively improves the removal rate of 
ammonia nitrogen, and can be flexibly adjusted.