Whereas serious health consequences of widespread consumption of groundwater elevated in As have been documented in several South Asian countries, the mechanisms responsible for As mobilization in reducing aquifers remain poorly understood. We document here a previously unrecognized and consistent relationship between dissolved As concentrations in reducing groundwater and the phosphate-mobilizable As content of aquifer sediment for a set of precisely depth-matched samples from across Bangladesh. The relationship holds across nearly 3 orders of magnitude in As concentrations and suggests that regional as well as local patterns of dissolved As in shallow groundwater are set by the solid phase according to a remarkably constant ratio of ∼250 μg/L dissolved As per 1 mg/kg P-mobilizable As. We use this relationship in a simple model of groundwater recharge to propose that the distribution of groundwater As in shallow aquifers of the Bengal Basin could primarily reflect the different flushing histories of sand formations deposited in the region over the past several thousand years.