Leachate, a highly polluted wastewater, is generated from landfill containing complex compositions which have great impact on the environment. The advanced treatment of biochemically treated landfill leachate using electrochemically assisted UV/chlorine process (UEC) in a flow reactor was investigated. The effects of pH and current density on COD and NH3-N removal by UEC process were evaluated. At the pH value of 5.0, current density of 60mA/cm2, the removal efficiencies for COD and NH3-N were observed as 77% and 87%, respectively. The electrochemical process alone (EC) could obtain relatively high NH3-N removal but very low COD removal, compared with which, the UEC process significantly promoted the removal efficiency of COD while that of NH3-N increased to a very limited extent. Most of NH3-N was converted into N2 and little nitrogen compounds and chloramines were remained in the leachate after 8h treatment. Moreover, the variations of active chlorine and chloride ions were monitored in the EC and UEC systems, and a possible mechanism was proposed for the UEC process. The in situ electro-generated active chlorine and photo-generated radical species should be responsible for the efficient degradation of landfill leachate. The total energy consumption and current efficiency were 216.5 (kWh/kg COD) and 17.5%, respectively, for 8h treatment. In addition, the molecular weight (MW) percentage distribution analysis and PARAFAC analysis of excitation emission matrix (EEM) fluorescence spectroscopy indicated that the organic matters in the leachate were significantly degraded into the fractions with small molecular weight.