Abstract The new opportunity given by the underground gasifier developed at Alcorisa in Spain (Province of Teruel) in the framework of an European experiment has promoted a better understanding of gasification in a natural reactor. The thermodynamical equilibria of gasification reactions and the repartition of the stable isotopes of carbon ( 13C/ 12C) in the produced gases have been used to monitor the process. An estimation of the temperatures inside the gasifier and at the exhaust has been performed. As shown by the isotopic balances, the tar formation is negligible or null and the pyrolysis zone spreads continuously. The study has confirmed the reality of the 13C isotopic abundance measurements for the system CO/CO 2 as an indicator of the temperature inside the gasifier. During the gasifier expansion, the temperature at the exhaust decreases whereas the temperature inside the gasifier is practically constant showing a slight increasing trend. As pointed out by the data, the oxygen enrichment of the gasifying agent plays an important role on the estimated temperatures.