This study explores linkages between the microbial composition and hydrochemical variables of pristine groundwater to identify active redox conditions and processes. Two confined aquifers underlying the city of Qianjiang in the Jianghan Plain in China were selected for this study, having different recharge sources and strong hydrochemical gradients. Typical methods for establishing redox processes according to threshold concentration criteria for geochemical parameters suggest iron or sulphate reduction processes. High‐throughput 16S rRNA sequencing was used to obtain diversity and taxonomic information on microbial communities. Instead of revealing iron‐ and sulphate‐reducing bacteria, salt‐ and alkali‐tolerant bacteria, such as the phylum Firmicutes and the class Gammaproteobacteria, and in particular, the family Bacillaceae, were dominant in the downstream groundwater of the first aquifer that had high ion concentrations caused by the dissolution of calcite and dolomite; meanwhile, the heterotrophic microaerophilic families Comamonadaceae and Rhodocyclaceae prevailed in the upstream groundwater of the first aquifer. Sulphate‐reducing bacteria were extremely abundant in the upstream groundwater of the second aquifer, as the SO42− concentration was especially high. Methanogens and methanotrophs were predominant in the downstream groundwater of the second aquifer even though the concentration of SO42− was much higher than 0.5 mg L−1. The microbial communities, together with the geochemical parameters, indicated that the upstream region of the first aquifer was suboxic, that Fe(III) and Mn(IV) reductions were not the main redox processes in the downstream groundwater of the first aquifer with high Fe and Mn concentrations, and that the redox processes in the upstream and downstream regions of the second confined aquifer were SO42− reduction and methanogenesis, respectively. This study expands understanding of the linkages between microbial communities and hydrogeochemistry in pristine groundwaters and provides more evidence for identifying active redox conditions and processes.