Abstract Carbon capture and storage (CCS) is broadly understood to be a key mitigation technology, yet modeling analyses provide different results regarding the applications in which it might be used most effectively. Here we use the Global Change Assessment Model (GCAM) to explore the sensitivity of CCS deployment across sectors and fuels to future technology cost assumptions. We find that CCS is deployed preferentially in electricity generation or in liquid fuels production, depending on CCS and biofuels production cost assumptions. We consistently find significant deployment across both sectors in all of the scenarios considered here, with bioenergy with CCS (BECCS) often the dominant application. As such, this study challenges the view that CCS will primarily be coupled with power plants and used mainly in conjunction with fossil fuels, and suggests greater focus on practical implications of significant CCS and BECCS deployment to inform energy system transformation scenarios over the 21st century.