The CO2 capture performance of sorbents derived from three distinct limestones, including a metamorphosed limestone, is studied under conditions relevant for calcium looping CO2 capture from power plant flue gas. The combined and individual influence of flue gas H2O and SO2 content, the influence of textural changes caused by sequential calcination/carbonation cycles, and the impact of CaSO4 accumulation on the sorbents’ capture performance were examined using bubbling fluidized bed reactor systems. The metamorphosed limestone-derived sorbents exhibit atypical capture behavior: flue gas H2O negatively influences CO2 capture performance, while limited sulfation can positively influence CO2 capture, with space time significantly impacting CO2 and SO2 co-capture performance. The morphological characteristics influencing sorbents’ capture behavior were examined using imaging and material characterization tools, and a detailed discussion is presented. This insight into the morphology responsible for metamorphosed limestone-derived sorbent’s anomalous capture behavior can guide future sorbent selection and design efforts.