Black shale oxidative weathering plays a significant role in a variety of processes including acid mine drainage and atmospheric CO₂ control. The modeling of weathering is highly dependent on reactive surface area. In this study it is shown that black shale oxidative weathering is regulated mainly by the external, geometrical surface area of rock polyhedrons and the organic matter’s (OM) internal surface area. The internal rock surface area decreases dramatically during OM dissolution from ∼15 m²/g to ∼5 m²/g. A linear relationship was found between the decrease of internal rock surface area and quantity of OM dissolved. Optical roughness analyses of black and bleached shale surface area reveal the formation of macropores due to the dissolution of mesoporous and probably microporous OM. However, due to deconsolidation, the geometrical external rock polyhedron surface area increases during weathering. Black shale polyhedrons show a doubling of their external surface area as OM decreases. This provokes an increase of the shale volume which is easily accessible by fluids. The increase of the external rock surface area seems to be self-accelerating during weathering. The upscaling of external and internal rock surface area evolution during weathering presented in this study demonstrates the possible application of these results to the improved understanding of a chemical transport in a variety of natural systems.