Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time, as long as they are acquired from waters where the dissolved inorganic carbon (DIC) is in isotope equilibrium with the atmospheric CO2. However, in shallow water platforms and epeiric settings, the influence of local to regional parameters on carbon cycling may lead to DIC isotope variations unrelated to the global carbon cycle. This may be especially true for the terminal Neoproterozoic, when Gondwana assembly isolated waters masses from the global ocean, and extreme positive and negative carbon isotope excursions are recorded, potentially decoupled from global signals. To improve our understanding on the type of information recorded by these excursions, we investigate the paired δ13Ccarb and δ13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior: the basal Bambuí Group. This succession represents a 1st-order sedimentary sequence and records two major δ13Ccarb excursions in its two lowermost lower-rank sequences. The basal cap carbonate interval at the base of the first sequence, deposited when the basin was connected to the ocean, hosts antithetical negative and positive excursions for δ13Ccarb and δ13Corg, respectively, resulting in Δ13C values lower than 25‰. From the top of the basal sequence upwards, an extremely positive δ13Ccarb excursion is coupled to δ13Corg, reaching values of +14‰ and −14‰, respectively. This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambuí Group that occurs with only minor changes in Δ13C values, suggesting change in the DIC isotope composition. We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles. This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis, favored by the basin restriction. The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere, resulting in a13C-enriched DIC influenced by methanogenic CO2. Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere, potentially affecting both the global carbon cycle and the climate.