Radiocarbon (14C) dating of sediment deposition around Antarctica is often challenging due to heterogeneity in sources and ages of organic carbon in the sediment. Chemical and thermochemical techniques have been used to separate organic carbon when microfossils are not present. These techniques generally improve on bulk sediment dates, but they necessitate assumptions about the age spectra of specific molecules or compound classes and about the chemical heterogeneity of thermochemical separations. To address this, the Rafter Radiocarbon Laboratory has established parallel ramped pyrolysis oxidation (RPO) and ramped pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) systems to thermochemically separate distinct carbon fractions, diagnose the chemical composition of each fraction, and target suitable RPO fractions for radiocarbon dating. Three case studies of sediment taken from locations around Antarctica are presented to demonstrate the implementation of combined RPO-AMS and Py-GC-MS to provide more robust age determination in detrital sediment stratigraphy. These three depositional environments are good examples of analytical and interpretive challenges related to oceanographic conditions, carbon sources, and other factors. Using parallel RPO-AMS and Py-GC-MS analyses, we reduce the number of radiocarbon measurements required, minimize run times, provide context for unexpected 14C ages, and better support interpretations of radiocarbon measurements in the context of environmental reconstruction.