In this paper, a laboratory-scale electrodialysis reactor with five compartment cells separated by a bipolar membrane and ion exchange membrane was assembled to remove ammonia nitrogen from landfill leachate as a pretreatment process. The effects of humic acid, magnesium ions (Mg2+) and calcium ions (Ca2+) existing in leachate on the removal efficiency of ammonium (NH4 +) were investigated by using simulated wastewater. The results indicate that humic acid has little impact on ammonium in the presence of an electric field. High concentrations of Mg2+ and Ca2+ in solution have a substantial impact on the removal efficiency of ammonium, but the average migration rate of the three ions is NH4 + > Mg2+ > Ca2+ under the same current intensity, and NH4 + plays a major role in electromigration for mixture electrodialysis. Therefore, ammonia nitrogen can be separated from leachate and accumulated effectively. Meanwhile, the bipolar membrane near the cathode produces alkali that is released into the base cell to promote ammonia nitrogen transformation from accumulated ammonium, which creates in-site alkaline condition for ammonia nitrogen recovery by a further stripping process. When the actual leachate collected from a local municipal sanitary landfill was employed, the reactor reached 86.17% of ammonia nitrogen removal after 3.0 h reaction. Analysis of membrane scale suggests the inhibitory effect of Mg2+ on Ca2+ migration during the initial working period of the reaction can potentially slow down the membrane scaling of the cation exchange membrane. This study provides a promising technology for the removal and recovery of ammonia nitrogen from landfill leachate.