The heterogeneous nature of upland hard-rock catchments in terms of geology, geomorphology, superficial deposits, soil type and land use gives rise to a range of hydrochemical characteristics in stream waters. This is further complicated by the large and often rapid changes in stream flow typical of storm events. The sources of solutes and flow pathways in hard-rock catchments are still poorly understood, in particular the role of bedrock groundwater. Spatial variations in water chemistry are presented for stream waters, soils and groundwaters in the forested Plynlimon catchment of Wales, UK. The results highlight a large degree of spatial heterogeneity in each of these systems. This has major implications for the application of end-member mixing analysis and presents serious problems for modelling in scaling up from study sites to catchment scale. However, such data provide important constraints on sources, flow pathways and residence times within individual catchment compartments, knowledge of which is essential for understanding how such catchments function. The characterisation of sub-surface waters in upland catchments requires a great deal of care during sampling as well as high spatial and temporal resolution of sampling, and further work is required to characterise the Plynlimon catchments fully. Nevertheless, the presence of an active and highly stratified groundwater system is considered important as a source of solutes and water to streams. It also provides a storage medium that is likely to make a major contribution to explaining the strongly damped rainfall Cl and d2H signals measured in the streams.