Oxy-fuel firing is a promising technology that should enable the capture and storage of anthropogenic CO2 emissions from large stationary sources such as power plants and heavy industry. However, this new technology has a high energy demand for air separation and CO2 compression and storage. Unresolved issues, such as determination of the optimal recycle location of flue gas, the flue gas cleaning steps required (SO2, NOx, and particles), and the impact of an oxy-fuel flue gas on the cleaning steps, also persist. The aim of this work was to study the performance of the wet flue gas desulfurization (FGD) process under operating conditions corresponding to oxy-fuel firing. The most important output parameters were the overall degree of desulfurization and the residual limestone concentration in the gypsum slurry. Pilot-scale experiments quantified that the introduction of a flue gas with 90 vol % CO2, at a holding tank pH 5.4, reduced the limestone dissolution rate significantly and thereby increased the residual, particulate limestone concentration in the gypsum slurry from 3.2 to 5.0 g/L slurry relative to a base-case (air-firing) experiment with a flue gas CO2 concentration around 7 vol %. In the same experiment, due to the higher residual limestone concentration, the degree of desulfurization increased from 91 to 94%. The addition of 10 mM adipic acid to the slurry was not sufficient to return the increased concentration of residual limestone to the base-case level, but an additional increase in desulfurization degree, from 94 to 97%, was obtained. Using a holding tank pH 5.0 (no adipic acid) returned both parameters to the levels observed in the base-case experiment.