Concentrations of both aluminium (Al) and dissolved organic carbon (DOC) in stream waters are likely to be regulated by factors that influence water flowpaths and residence times, and by the nature of the soil horizons through which waters flow. In order to investigate landscape-scale spatial patterns in streamwater Al and DOC, we sampled seven streams draining the Hubbard Brook valley in central New Hampshire. We observed considerable variation in stream chemistry both within and between headwater watersheds. Across the valley, concentrations of total monomeric aluminium (Alm) ranged from below detection limits (<0·7 µmol l−1) to 22·3 µmol l−1. In general, concentrations of Alm decreased as pH increased downslope. There was a strong relationship between organic monomeric aluminium (Alo) and DOC concentrations (R2 = 0·92). We observed the highest Alm concentrations in: (i) a watershed characterized by a steep narrow drainage basin and shallow soils and (ii) a watershed characterized by exceptionally deep forest floor soils and high concentrations of DOC. Forest floor depth and drainage area together explained much of the variation in ln Alm (R2 = 0·79; N = 45) and ln DOC (R2 = 0·87; N = 45). Linear regression models were moderately successful in predicting ln Alm and ln DOC in streams that were not included in model building. However, when back-transformed, predicted DOC concentrations were as much as 72% adrift from observed DOC concentrations and Alm concentrations were up to 51% off. This geographic approach to modelling Al and DOC is useful for general prediction, but for more detailed predictions, process-level biogeochemical models are required. Copyright © 2005 John Wiley & Sons, Ltd.