The Paleocene-Eocene thermal maximum (PETM) has been attributed to a sudden release of carbon dioxide and/or methane. 40Ar/39Ar age determinations show that the Danish Ash-17 deposit, which overlies the PETM by about 450,000 years in the Atlantic, and the Skraenterne Formation Tuff, representing the end of 1 +/- 0.5 million years of massive volcanism in East Greenland, are coeval. The relative age of Danish Ash-17 thus places the PETM onset after the beginning of massive flood basalt volcanism at 56.1 +/- 0.4 million years ago but within error of the estimated continental breakup time of 55.5 +/- 0.3 million years ago, marked by the eruption of mid-ocean ridge basalt-like flows. These correlations support the view that the PETM was triggered by greenhouse gas release during magma interaction with basin-filling carbon-rich sedimentary rocks proximal to the embryonic plate boundary between Greenland and Europe.