Landfill leachate is challenging to treat due to its complex composition. Advanced oxidation processes such as Fenton process can be effective to treat leachate. Herein, a previously developed membrane electrochemical reactor (MER) was coupled with Fenton oxidation through providing synergistic benefits with the low solution pH, reduced organics, and ammonia removal/recovery. This two-stage coupled system reduced the leachate COD by 88%, much higher than that from the standalone Fenton process treating raw leachate. In addition, the usage of chemical reagents has been greatly reduced. At a dimensionless oxidant dose of 1.0, the coupled MER-Fenton system reduced the consumption of both FeSO4⋅7H2O and H2O2 by 39%, H2SO4 by 100%, and NaOH by 55%. Consequently, the sludge production was reduced by 51% in weight and 12% in volume. Despite electricity consumption by the MER, the coupled system cost $4.76 per m3 leachate less than the standalone Fenton treatment. More notably, direct Fenton oxidation removed only 21% of ammonia; in comparison the MER-Fenton system removed ammonia by 98% with the possibility for recovery at a rate of 30.6–55.2 kg N m−3 reactor d−1. Those results demonstrate that coupling MER with Fenton process could mitigate some inherent drawbacks of Fenton oxidation such as ineffective ammonia removal, high acid and chemical reagents dose requirements, and a large amount of sludge generation. This system may be moved towards practical applications by addressing a few challenges such as using renewable energy to power MER.