Calcite dissolution and Ca–Mg ion exchange on carbonate rock surfaces have been proposed as potential mechanisms occurring during smart waterflooding in carbonate reservoirs. However, there is still a lack of fundamental understanding of these reactions to quantitatively evaluate their effects in the reservoir flooding process. Especially, the data on precipitation and dissolution kinetics are insufficient. In this work, the equilibration kinetics of calcite dissolution and Ca–Mg exchange was experimentally studied. The behavior of three powders was compared: pure calcium carbonate, Stevns Klint outcrop chalk, and North Sea reservoir chalk. It was found that the equilibration time for calcite dissolution was of the order of seconds for a given surface-area-to-liquid-volume ratio. The existing theory of calcite dissolution could well reproduce our observations. The Ca–Mg exchange showed two-step kinetics: the first step was fast, and it dominated the process within the first hour of reaction; the second step was slow, and it continued longer than the time of observation (2 weeks). Characteristic times for the two steps were extracted by fitting the experimental curves. A two-layer adsorption model was proposed to characterize the kinetic process and successfully matched with experimental data. The findings were further extended to flow-through scenarios. By comparing with literature data and surface complexation models, it was concluded that calcite dissolution alone was unlikely to be able to explain the additional recovery reported in the literature. The Ca–Mg exchange process could dominate the fluid–rock interactions at a high temperature in pure calcium carbonate rocks, while competitive adsorption of cations appeared to control the process at a lower temperature. Different carbonate rocks possess different properties with regard to the ion-exchange process.