A regional assessment of water quality in small streams was conducted within four areas of distinct physiography and lithology in the upper Potomac River Basin. The Potomac River is a major tributary to the Chesapeake Bay, and this study provides new insight on the relationships between nutrient concentrations in small streams and watershed characteristics within this river basin. Nutrient concentrations were compared to land-use data including categories for agriculture (cropland and pasture), urban areas, and forests. Among agricultural areas, streams draining areas of intense row cropping typically contained higher nitrate concentrations than did those draining pastures. Streams draining forested areas typically had the lowest nutrient concentrations. Streams in areas underlain by carbonate bedrock were more likely to contain elevated concentrations of inorganic nitrogen and potassium than did streams in areas underlain by fractured siliciclastic or crystalline rocks, and we suggest that this is a physical phenomenon related to high hydraulic conductivities in carbonate ground-water systems. The median nitrate concentrations were highest in the Great Valley portion of the Valley and Ridge physiographic province, particularly in watersheds that have both carbonate bedrock and intensive row cropping. Values of nitrate in these streams ranged up to 8.99 mg/L as nitrogen. The soluble phosphorus concentrations during baseflow were generally low in all subunits, even in some settings with potential for high phosphorus inputs such as urban areas with municipal point sources or agricultural areas. The mobility of phosphorus in these environments may be hindered by adsorption and geochemical reactions.