Stable carbon-isotope compositions of pedogenic carbonate occurring in three clay-rich vertic paleosols within Paleozoic red-bed successions in central Pennsylvania provide a record of past pedogenic environments and can be used to estimate CO2 pressure (PCO2) of the Paleozoic atmosphere. The δ13C values of carbonate nodules from paleosols in the deltaic lower Bloomsburg Formation (Upper Silurian) reflect the contribution of carbon from marine groundwater or fossils, coupled with low biological activity. The δ13C values of carbonate rhizocretions from stratigraphically high paleosols in the Bloomsburg Formation, and in the alluvial Catskill (Upper Devonian) and Mauch Chunk (Upper Mississippian) Formations, suggest an extensive C3 flora and significant contribution of atmospheric CO2. Paleozoic atmospheric CO2 levels inferred from δ13C of pedogenic carbonate are significantly higher than present levels.