Doping Pt/ceria catalysts with alkali metals was found to lead to an important weakening of the formate C–H bond, as demonstrated by a shift to lower wavenumbers of the ν(CH) vibrational mode. However, with high alkalinity (∼2.5%Na or equimolar amounts of K, Rb, or Cs), a tradeoff was observed such that while the formate became more reactive, the stability of the carbonate species, which arises from the formate decomposition, was found to increase. This was observed by TPD-MS measurements of the adsorbed CO2 probe molecule. Increasing the amount of alkali to levels that were too high also led to lower catalyst BET surface area, the blocking of the Pt surface sites as observed in infrared measurements, and also a shift to higher temperature of the surface shell reduction step of ceria during TPR. When the alkalinity was too high, the CO conversion rate during water–gas shift decreased in comparison with the undoped Pt/ceria catalyst. However, at lower levels of alkali, the abovementioned inhibiting factors on the water–gas shift rate were alleviated such that the weakening of the formate C–H bond could be utilized to improve the overall turnover efficiency during the water–gas shift cycle. This was demonstrated at 0.5%Na (or equimolar equivalent levels of K) doping levels. Not only was the formate turnover rate found to increase significantly during both transient and steady state DRIFTS tests, but this effect was accompanied by a notable increase in the CO conversion rate during low temperature water–gas shift.