Carbon capture and storage (CCS) is a strategy that is used to reduce global greenhouse gas emissions. As a result of increased government incentives and maturing carbon markets, CCS is currently experiencing an unprecedented level of public and commercial interest. In the United States, the Appalachian Basin contains abundant hydrocarbon resources and is the location of numerous industrial facilities, making the region a promising target for CCS development. However, the lack of seismic reflection surveys and well data, along with complex geologic structure throughout much of the basin, has limited the commercial interest in CCS development. This study proposes that the thin-skinned fold-and-thrust belt of the Appalachian Basin may contain geology suitable for secure long-term CO2 storage. This region, known as the Valley and Ridge physiographic province, holds complex fold-and-thrust structures that may effectively trap commercial volumes of CO2. We test this idea by developing a suite of kinematically feasible geologic interpretations for the Catawba syncline Pulaski thrust system in southwest Virginia. We then use these geologic models to conduct numerical simulations for CO2 storage within the fold-and-thrust belt structures of the Catawba syncline. Our simulation results indicate that the geometric configuration of fold-and-thrust belt structures may offer commercially viable CO2 traps for CCS projects within the Appalachian Basin and similar geologic settings worldwide.