An electrocatalytic hydrophobic membrane was prepared by vacuum filtration method, and a novel electro-Fenton membrane distillation (EF-MD) composite process was developed based on electrocatalytic hydrophobic membrane coupled with gas-sweeping membrane distillation and electro-Fenton technology. The performance of hydrogen peroxide production by electrocatalytic hydrophobic membrane and the influencing factors of EF-MD process were investigated. The experimental results showed that the H_2O_2 yield was up to 126 mg/L at a current intensity of 160 mA, a ferrous iron concentration of 1.0 mmol/L, a feed liquid temperature of 60 ℃, a sulfate concentration of 0.05 mol/L, a pH of 3, a purge gas of O_2 and a flow rate of 2 L/min. The degradation rate of 0.5 mmol/L glyphosate could reach over 99% within 100 hours, the TOC removal rate could reach 95%, the membrane flux was stable at 2.37 kg/(m^2·h), and the salt rejection rate could be maintained at 99.88%, with the feed liquid salt concentration increasing from 7.1 g/L to 38.9 g/L. The successful construction of the EFMD composite process demonstrated that this new process could achieve the advanced treatment and concentration reduction of glyphosate wastewater simultaneously in the same reaction unit, which provided a new solution for membrane fouling and membrane wetting problems during the operation of membrane distillation.