There is a considerable body of evidence to support the contention that the atmospheric Pb burden is now considerably greater than it was in the remote past. However, as there are a diversity of potential environmental pathways leading to Pb ingestion, it is not clear how atmospheric Pb levels relate to human exposure. It is necessary to establish a baseline for human exposure to Pb from natural sources in the pre-metallurgical past, with which contemporary exposure can be compared. This paper addresses this issue by comparing the Pb content of human dental enamel — an established proxy for Pb exposure — from modern and archaeological, pre-metallurgical individuals using thermal and plasma ionisation mass spectrometry. It is shown that mean Neolithic enamel Pb contents are approximately 0.31±0.04 ppm. These values are only one order of magnitude lower than previously reported data for the same tissues for modern juveniles, despite an established 400-fold increase in the atmospheric Pb burden. The results suggest that ‘natural’ exposure to Pb in food and water may have been higher than previously thought, and that the link between atmospheric Pb and human exposure warrants further investigation.