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The thermal degradation of kerogen during pyrolysis in the presence and absence of pyrite as an additive was investigated and discussed from a free-radical chemistry standpoint using in situ ESR techniques. The added pyrite has pronounced effects on the activity of free radicals of kerogen samples representing the diagenesis stage. In this stage, pyrite enhances and accelerates the process of free-radical formation, where the generation of free radicals in kerogen, in the presence of added pyrite, starta at temperature lower than those observed in its absence. On the contrary, pyrite has negligible effects on the formation of free radicals in kerogen samples representing the catagenesis stage. The overall increase of free-radical activity in the presence of pyrite is consistent with the conversion of pyrite to pyrrhotite. It is suggested that pyrite acts indirectly as a catalyst through the nascent sulfur produced from the pyrite to pyrrhotite conversion process.