Knowledge of the hydrochemical dynamics of the trace metal manganese (Mn) in upland catchments is required for water quality management. Stream water Mn and other solutes and flow were monitored in two upland catchments in northern England with different soils: one dominated by peat (HS7), the other by mineral soils (HS4). Maximum Mn concentrations occurred at different times in the two catchments: in summer baseflow at HS4 and during late summer storm events at HS7. A two-component chemical mixing model was used to identify the hydrological processes controlling Mn concentrations in stream water. This approach was more successful for HS4 than HS7, probably because of different processes of Mn release in the two catchments and also difficulties in selecting conservative solutes. Factor analysis of the stream water chemistry data set for each catchment was more useful in identifying the controls on Mn release into runoff. The factors indicate that the main source of Mn at HS4 is the hydrological pathway supplying summer baseflow, whereas at HS7 Mn is released during the rewetting of dried peat soils. Manganese concentrations in stream water in upland catchments appear to depend on soil type and antecedent moisture conditions. This has implications for the design of sampling strategies in upland catchments and also for managing the quality of water supplies from such areas.