A hydrological reconnaissance study in a first-order tropical rainforest catchment in western Amazonia implicated overland flow as an important hydrological pathway. A complementary hydrometric and hydrochemical approach that involved the recording of overland flow hydrographs and the determination of streamflow, overland flow, groundwater, soil water, and throughfall chemical signatures, was essential to establish unambiguously the importance of this pathway. Largely uncontrolled by topography, overland flow does occur in any season, regardless of antecedent moisture conditions, which only influence the volumes generated. The latter effect is also reflected in a close approximation of stormflow and overland flow chemical signatures, as expressed in the K 2 ratio. We conclude that, despite its greater logistical demands, a complementary hydrometric/hydrochemical approach is essential to understand a catchment's hydrological behaviour, especially where fast pathways are at work; such pathways are apparently common in more forest ecosystems than has been previously assumed.