There is growing concern regarding human dietary exposure to arsenic (As) via consumption of rice. The concentration and speciation of As in rice are highly variable, and models describing rice As speciation as a function of environmental covariates remain elusive. We conducted a survey of paddy rice and soil in the Mekong Delta with the objective of linking patterns in rice As content to soil chemical variables or hydrogeological parameters. The sum of As species (ΣAs) in husked rice averaged 243 μg/kg and the average inorganic As (iAs) content was 84%. There was no relationship found between rice As concentration or speciation and As levels in soil. However, mean As concentrations in groundwater near rice sampling locations were strongly correlated with grain ΣAs and iAs over a large part of the study region, despite the fact that groundwater is not commonly used for rice paddy irrigation in this region. We hypothesize that surficial sediments with high concentrations of soluble and plant-available As also serve as sources of arsenic to downgradient shallow aquifers, explaining the observed associations between rice and groundwater As. This study suggests that shallow groundwater As concentrations may serve as a useful indicator for locations at risk of elevated iAs concentrations in rice.