Temporal changes of dominant microbial populations in groundwater in response to the leachate from Shanghai Laogang Landfill were investigated. Concentrations of dissolved redox-relevant species in groundwater suggested that the dominating redox process had changed from denitrification to methane-production/sulfate-reduction due to landfilling. Dominant microbial populations were determined using restriction fragment length polymorphism(RFLP) analyses of 16S rRNA gene libraries, which were further studied by sequencing and phylogenetic analyses. The results indicated that obvious shifts of dominant microbial populations had occurred in groundwater in response to the pollution of leachate. The closest relatives of some dominant clones are accordant with the dominating redox processes determined by hydrochemical analyses, based on the GenBanks indications on the ability to perform redox reactions.