A description is given of the hydrological regime and associated surface water quality recorded at a multi-disciplinary long-term investigation into the effects of acid precipitation and afforestation. The study catchment at Loch Dee is situated on the margins of the Loch Doon granite complex in SW Scotland. Annual rainfall is in excess of 2200 mm. The three main tributary burns exhibit a rapid response to rainfall with a high percentage of direct runoff. The loch with an average volume of 3650 M1 and a contributing catchment area of 15·6 km2 has an average turn-over of approximately forty days but this has varied from 15 to 100 days. Local physical variations are shown to influence both hydrological response and surface water quality. Generally stream water during spate conditions reflects rainfall chemistry. Occasionally, however, moderately acid rainfall containing large concentrations of sea salts has produced highly acidic runoff through a process of ion-exchange within the surface horizons of the soils. The quality of base flows shows a spatial variation which reflects various lithologies to the extent that pH values ranging from 4·9 to 6·9 have been observed.