Constraining past fluctuations in global temperatures is central to our understanding of the Earth's climatic evolution. Marine proxies dominate records of past temperature reconstructions, whereas our understanding of continental climate is relatively poor, particularly in high-latitude areas such as Antarctica. The recently developed MBT/CBT (methylation index of branched tetraethers/cyclization ratio of branched tetraethers) paleothermometer offers an opportunity to quantify ancient continental climates at temporal resolutions typically not afforded by terrestrial macrofloral proxies. Here, we have extended the application of the MBT/CBT proxy into the Cretaceous by presenting paleotemperatures through an expanded sedimentary succession from Seymour Island, Antarctica, spanning the latest Maastrichtian and Paleocene. Our data indicate the existence of a relatively stable, persistently cool temperate climate on the Antarctic Peninsula across the Cretaceous-Paleogene boundary. These new data help elucidate the climatic evolution of Antarctica across one of the Earth's most pronounced biotic reorganizations at the Cretaceous-Paleogene boundary, prior to major ice-sheet development in the late Paleogene. Our work emphasizes the likely existence of temporal and/or spatial heterogeneities in climate of the southern high latitudes during the early Paleogene.