Groundwater biogeochemistry is adversely impacted when municipal solid waste leachate, rich in nutrients and anthropogenic compounds, percolates into the subsurface from leaking landfills. Detecting leachate contamination using statistical techniques is challenging because well strategies or analytical techniques may be insufficient for detecting low levels of groundwater contamination. We sampled profiles of the microbial community from monitoring wells surrounding a leaking landfill using terminal restriction fragment length polymorphism (T‐RFLP) targeting the 16S rRNA gene. Results show in situ monitoring of bacteria, archaea, and the family Geobacteraceae improves characterization of groundwater quality. Bacterial T‐RFLP profiles showed shifts correlated to known gradients of leachate and effectively detected changes along plume fringes that were not detected using hydrochemical data. Experimental sediment microcosms exposed to leachate‐contaminated groundwater revealed a shift from aβ‐Proteobacteria and Actinobacteria dominated community to one dominated by Firmicutes andδ‐Proteobacteria. This shift is consistent with the transition from oxic conditions to an anoxic, iron‐reducing environment as a result of landfill leachate‐derived contaminants and associated redox conditions. We suggest microbial communities are more sensitive than hydrochemistry data for characterizing low levels of groundwater contamination and thus provide a novel source of information for optimizing detection and long‐term monitoring strategies at landfill sites.