Recently, the role of ceria vacancies on water–gas shift activity has been explained in terms of a redox mechanism, whereby CO adsorbed on a metal reduces the ceria surface to generate CO2, and water reoxidizes the ceria surface to CeO2, liberating hydrogen in the process. In this study, we examine the possibility of a ceria-mediated redox mechanism by examining more closely the evolution of carbonate and formate bands under different controlled treatment environments, and utilizing different reduction procedures. Earlier it was claimed that the decomposition of carbonates by water was consistent with a redox process, whereby the CO2 product could spillover to the support. We found that the observation of carbonate formation and decomposition by water was a result of the treatment procedure used in the earlier work, and that, once bridging OH groups are produced in the presence of water, the reaction more likely proceeds via a formate intermediate, which is produced by reaction of CO with the active bridging OH groups. However, the vacancies appear to play an important role in generating these active sites. Possible pathways to active site generation are discussed.