While chemical weathering has not always been considered an active process in the McMurdo Dry Valleys (MDV), Antarctica, long‐term geochemical and hydrological investigations have provided an overall better understanding of chemical weathering in this polar desert environment. Liquid water on the landscape is limited to stream channels as well as shallow subsurface melt features, as there is no overland flow. Stream total suspended sediment loads are low, with the sources of sediment from stream channels, aeolian input, and/or from the surfaces of glaciers. MDV soils contain high concentrations of soluble salts with little clay material, but since absent of water, these soils are a minimal location of chemical weathering. Hyporheic zones exchange water during streamflow, and these areas control the stream geochemistry over various temporal scales. Hyporheic zones promote rapid aluminosilicate weathering by moving dilute glacial meltwater into intimate contact with sediment surfaces. Rapid weathering of the aluminosilicates in the streambed and hyporheic zones is the most plausible explanation for chemostasis observed in these streams, indicating that little to no catchment processes are necessary to explain the observed chemostasis in the MDV. Shallow subsurface waters with distinct geochemical signatures have much higher dissolved Si concentrations than the stream waters and indicate that they are responsible for enhanced aluminosilicate weathering in this polar desert environment. The dissolution of CaCO₃ is also a major process in the hyporheic zones as generally the streams are unsaturated with respect to calcite. Cation‐exchange reactions are also important in the evolution from Na‐Cl brines to Ca‐Cl brines within the soil column, while authigenic CaCO₃ can both dissolve and precipitate depending on the condition of the system. Recently, stream channel landscapes are changing due to the melting of buried ice, creating thermokarst and water track features, resulting in a sediment and solute influx to the stream.