Monitoring the effects of acidic deposition on aquatic ecosystems in the Northeastern US has generally required regular measurements of stream buffering chemistry (i.e. acid-neutralizing capacity (ANC) and calcium Ca2+), which can be expensive and time consuming. The goal of this paper was to develop a simple method for predicting baseflow buffering chemistry based on the hydrogeomorphic properties of ten nested watersheds in the Neversink River basin (2·0–176·0 km2), an acid-sensitive basin in the Catskill Mountains, New York State. The tributaries and main reach watersheds have strongly contrasting mean baseflow ANC values and Ca2+ concentrations, despite rather homogeneous vegetation, bedrock geology, and soils. A stepwise regression was applied to relate 13 hydrogeomorphic properties to the mean baseflow ANC values and Ca2+ concentrations. The regression analysis showed that watersheds with lower ANC values had a higher mean ratio of ‘quickflow’ runoff to precipitation during 20 non-snowmelt runoff events (referred to as mean runoff ratio). The mean runoff ratio could explain at least 80% of the variability in mean baseflow ANC values and Ca2+ concentrations among the ten watersheds. Greater mean runoff ratios also correlated with steeper slopes and greater drainage densities, thus allowing the prediction of baseflow ANC values (r2 = 0·75) and Ca2+ concentrations (r2 = 0·77) with widely available spatial data alone. These results indicate that hydrogeomorphic properties can predict a watershed's sensitivity to acid deposition in regions where the spatial sources of stream buffering chemistry from the bedrock mineralogy and soils are fairly uniform. Copyright © 2010 John Wiley & Sons, Ltd.