The interplay between the hydrologic processes that supply, store, and route water in catchment systems and the chemical weathering reactions that add and remove solutes acts as an important control on chemical weathering fluxes. In this study, we use paired measurements of solute chemistry and runoff in four nested catchments that span the transition from the Andes Mountains to the Amazonian foreland floodplain in Peru in order to investigate the links between hydrology and weathering processes and to determine how these links change across a geomorphic gradient. All of the sites show variation in elemental concentrations and ratios with runoff consistent with hydrologically driven changes in lithologic sources, the extent of secondary mineral precipitation, and, potentially, fluid flow paths. In the Andean sites, solute concentrations are relatively constant despite large changes in runoff. This is in direct contrast to the foreland floodplain site, where solute concentrations are diluted as runoff increases. In the Andes–Amazon, the concentration–runoff behavior is correlated with the mean catchment slope angle, which suggests that erosional processes, by modulating the timescales over which weathering reactions occur within the critical zone, can be an underlying control on solute production and therefore on chemical weathering. Due to the co-variation between the geomorphic and hydrologic controls on chemical weathering, weathering fluxes in Andean sites are more sensitive to seasonal changes in runoff than in the foreland floodplain site.