Understanding the chemical character and turnover time of the oldest soil organic carbon (SOC) fraction is fundamental in deciphering soil carbon sequestration processes and the fate of soil-eroded carbon in aquatic sediments. Two main processes are thought to extend the turnover time of SOC: protection by the mineral matrix and chemical recalcitrance. Various oxidation methods have been proposed to isolate the oldest and most recalcitrant SOC fraction, which is often assumed to be black carbon (BC). However, few data have been published that confirm the chemical character of the isolated fractions. Using established and newly developed methods together with 13C-NMR spectroscopy and AMS dating, we show that protection by the mineral matrix prolonged the turnover time of SOC by tens of years, but long-term (hundreds of years) stabilization was controlled by the inherent recalcitrance of SOC, determined by the type of ecosystems. In ecosystem without significant fire occurrences, the older SOC pool was comparably small and was represented by alkyl carbon. In ecosystems with high fire frequency charcoal constituted the oldest SOC pool, and constituted up to 35% of the total SOC. By applying methods with different oxidative strengths, it was possible to isolate different age groups of charcoal with different degrees of weathering. Further substantiation of this finding could provide a much greater resolution of paleo-fire events. Our results demonstrate that fire frequency plays a dominant role in determining the chemical nature and 14C abundance of SOC and that the separation of age groups of charcoal provides a means to reconstruct detailed fire histories. Our results indicate that modeling SOC turnover, transport and sequestration for frequently burnt environments requires modification of existing models, specifying an input and decay function for the charcoal pool in different environments.