[Objective] The leakage of leachate from a landfill can cause severe groundwater contaminations. Characterization the spatial distribution of the landfill-derived contamination plume is crucial for site remediation and pollution investigation. [Methods] In this paper, a typical case of groundwater pollution investigation at a landfill in Hubei is combined with the implementation of a six-layer groundwater multilevel sampling well (-6m、-8m、-10m、-12m、-16m、-20m), and 14 sets of groundwater chemical samples as well as other hydrogeological survey data to reveal the hydrogeochemical spatial distribution of the contaminated groundwater. [Results] The results indicate that the concentrations of most ions in groundwater such as TDS, COD (Mn), Mg2+, HCO3- and Cl- decrease linearly with increasing vertical depth, thus indicating that surface rainfall infiltration and anthropogenic pollution are the controlling influences on the shallow groundwater. The concentration of NH4+, NO3-, NO2-, Mn, Ni and other ions increases linearly with increasing vertical depth, reflecting groundwater chemical field under the control of natural geological condition and water-rock interaction. In addition, the correlation coefficient matrix analysis characterises the stratified distribution of groundwater chemical components, the correlation coefficient between the groundwater sample from the U-tube groundwater multilevel sampling well and other conventional shallow boreholes decreases from 0.984 to 0.566.[Conclusions]The conclusion indicates that the novel groundwater multilevel sampling technology has the ability, to characterize the hydrogeochemical spatial distribution of groundwater along the vertical depth of the geological layers, to differentiate and reveal the impacts of natural geological factors and human-made pollution, thus to identify the spatial distribution of groundwater plumes. In a word, the groundwater multilevel sampling technology could provide quantities’ data and accurate guidance for site-scale groundwater pollution remediation and risk management.