A 2 to 4 °C warming episode, known as the Latest Maastrichtian warming event (LMWE), preceded the Cretaceous-Paleogene boundary (KPB) mass extinction at 66.05 ± 0.08 Ma and has been linked with the onset of voluminous Deccan Traps volcanism. Here, we use direct measurements of melt-inclusion CO2 concentrations and trace-element proxies for CO2 to test the hypothesis that early Deccan magmatism triggered this warming interval. We report CO2 concentrations from NanoSIMS and Raman spectroscopic analyses of melt-inclusion glass and vapor bubbles hosted in magnesian olivines from pre-KPB Deccan primitive basalts. Reconstructed melt-inclusion CO2 concentrations range up to 0.23 to 1.2 wt% CO2 for lavas from the Saurashtra Peninsula and the Thakurvadi Formation in the Western Ghats region. Trace-element proxies for CO2 concentration (Ba and Nb) yield estimates of initial melt concentrations of 0.4 to 1.3 wt% CO2 prior to degassing. Our data imply carbon saturation and degassing of Deccan magmas initiated at high pressures near the Moho or in the lower crust. Furthermore, we find that the earliest Deccan magmas were more CO2 rich, which we hypothesize facilitated more efficient flushing and outgassing from intrusive magmas. Based on carbon cycle modeling and estimates of preserved lava volumes for pre-KPB lavas, we find that volcanic CO2 outgassing alone remains insufficient to account for the magnitude of the observed latest Maastrichtian warming. However, accounting for intrusive outgassing can reconcile early carbon-rich Deccan Traps outgassing with observed changes in climate and atmospheric pCO2.