Capturing CO2 from large-scale power generation combustion systems such as fluidized bed combustors (FBCs) may become important in a CO2-constrained world. Using previous experience in capturing pollutants such as SO2 in these systems, we discuss a range of options that incorporate capture of CO2 with CaO in FBC systems. Natural limestones emerge from this study as suitable high-temperature sorbents for these systems because of their low price and availability. This is despite their limited performance as regenerable sorbents. We have found a range of process options that allow the sorbent utilization to maintain a given level of CO2 separation efficiency, appropriate operating conditions, and sufficiently high power generation efficiencies. A set of reference case examples has been chosen to discuss the critical scientific and technical issues of sorbent performance and reactor design for these novel CO2 capture concepts.