The generative gas potential of the Mississippian Barnett Shale in the Fort Worth Basin, Texas, was quantitatively evaluated by sealed gold-tube pyrolysis. Kinetic parameters for gas generation and vitrinite reflectance (Ro) changes were calculated from pyrolysis data and the results used to estimate the amount of gas generated from the Barnett Shale at geologic heating rates. Using derived kinetics for Ro evolution and gas generation, quantities of hydrocarbon gas generated at Ro ∼ 1.1% are about 230 L/t (7.4 scf/t) and increase to more that 5800 L/t (186 scf/t) at Ro ∼ 2.0% for a sample with an initial total organic carbon content of 5.5% and Ro = 0.44%. The volume of shale gas generated will depend on the organic richness, thickness, and thermal maturity of the shale and also the amount of petroleum that is retained in the shale during migration. Gas that is reservoired in shales appears to be generated from the cracking of kerogen and petroleum that is retained in shales, and that cracking of the retained petroleum starts by Ro ∼ 1.1%. This result suggests that the cracking of petroleum retained in source rocks occurs at rates that are faster than what is predicted for conventional siliciclastic and carbonate reservoirs, and that contact of retained petroleum with kerogen and shale mineralogy may be a critical factor in shale-gas generation. Shale-gas systems, together with overburden, can be considered complete petroleum systems, although the processes of petroleum migration, accumulation, and trap formation are different from what is defined for conventional petroleum systems.