An integrative methodology, including controlled heating experiments, petrography, taphonomy, systematics of charcoal fragments, solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), and 14 C dating, are used to discriminate in situ (anthropogenic) versus transported charcoal accumulations in the Ancestors Chamber at the Aktun Ha cenote and its potential relationship with the initial settlement of the Yucatán Peninsula in Mexico. Rock heating experiments demonstrated changes in color, weight loss, and recrystallization fabrics under temperatures from 200°C to 900°C. At temperatures of up to 600°C, calcite changed to portlandite. Taphonomic examination of the charcoal revealed that the fragments were not transported by water. Anatomical studies of the charcoal revealed the presence of species similar to modern examples used as fuel. The solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy confirmed different aromatization degrees, and DSC provided information related to the hearth shape and combustion conditions throughout the thermal event. The 14 C ages determined