Petroleum (oil and gas) forms from the bacterial or thermal breakdown of kerogen during progressive burial in sedimentary basins. During times of petroleum generation, kerogens in organic-rich source rocks expel petroleum to form a fluid phase in the pore system, capable of migrating under hydrodynamic and buoyancy forces to ultimately escape to the surface or accumulate within petroleum traps in the subsurface. The relative timing of petroleum charge and trap formation is a vital component in the accumulation of petroleum deposits. Exhumed basins have been historically viewed as higher-risk targets for conventional petroleum exploration because of, inter alia, the switch-off of petroleum generation in the source rock at the commencement of cooling during exhumation. However, even at the switch-off point, the source rock may retain a significant volume of petroleum sorbed in kerogen and within its pore system. Herein we demonstrate that if the source rock is exhumed to shallower depths after peak burial, pore pressure reduction and the associated volumetric expansion of the petroleum—particularly of the gaseous—phase in the pore system will result in the discharge of additional petroleum into the adjacent carrier bed or reservoir formations. Because most onshore sedimentary basins are characterized by major exhumation events at some point in their history, this represents an additional and underappreciated mechanism for a late-stage petroleum charge in exhumed sedimentary basins. The modeling also indicates that both the initial, pre-exhumation, total gas storage capacity and the exhumation gas charge are likely to be volumetrically more significant for gas-bearing source rocks that have been exposed to higher initial pressures and lower thermal gradients. The concepts presented here also have implications for petroleum resources retained within unconventional shale reservoirs because high-graded shale plays may be associated with systems where the magnitude or rate of relative overpressure dissipation has limited exhumation charge from the unconventional to conventional reservoirs within the basin.