Dramatic warming and upheaval of the carbon system at the end of the Paleocene Epoch have been linked to massive dissociation of sedimentary methane hydrate. However, testing the Paleocene-Eocene thermal maximum hydrate dissociation hypothesis has been hindered by the inability of available proxy records to resolve the initial sequence of events. The cause of the Paleocene-Eocene thermal maximum carbon isotope excursion remains speculative, primarily due to uncertainties in the timing and duration of the Paleocene-Eocene thermal maximum. We present new high-resolution stable isotope records based on analyses of single planktonic and benthic foraminiferal shells from Ocean Drilling Program Site 690 (Weddell Sea, Southern Ocean), demonstrating that the initial carbon isotope excursion was geologically instantaneous and was preceded by a brief period of gradual surface-water warming. Both of these findings support the thermal dissociation of methane hydrate as the cause of the Paleocene-Eocene thermal maximum carbon isotope excursion. Furthermore, the data reveal that the methane-derived carbon was mixed from the surface ocean downward, suggesting that a significant fraction of the initial dissociated hydrate methane reached the atmosphere prior to oxidation.