The partitioning of CO2 between atmosphere and ocean depends to a large degree not only on the amount of dissolved inorganic carbon (DIC) but also on alkalinity in the surface ocean. That is also why ocean alkalinity enhancement (OAE) is discussed as one potential approach in the context of negative emission technologies. Although alkalinity is thus an important variable of the marine carbonate system, little knowledge exists on how its representation in models compares with measurements. We evaluated the large-scale alkalinity distribution in 14 CMIP6 Earth system models (ESMs) against the observational data set GLODAPv2 and show that most models, as well as the multi-model mean, underestimate alkalinity at the surface and in the upper ocean and overestimate it in the deeper ocean. The decomposition of the global mean alkalinity biases into contributions from (i) physical processes (preformed alkalinity), which include the physical redistribution of biased alkalinity originating from the soft tissue and carbonates pumps; (ii) remineralization; and (iii) carbonate formation and dissolution showed that the bias stemming from the physical redistribution of alkalinity is dominant. However, below the upper few hundred meters the bias from carbonate dissolution can gain similar importance to physical biases, while the contribution from remineralization processes is negligible. This highlights the critical need for better understanding and quantification of processes driving calcium carbonate dissolution in microenvironments above the saturation horizons and implementation of these processes into biogeochemical models. For the application of the models to assess the potential of OAE to increase ocean carbon uptake, a back-of-the-envelope calculation was conducted with each model's global mean surface alkalinity, DIC, and partial pressure of CO2 in seawater (pCO2) as input parameters. We evaluate the following two metrics: (1) the initial pCO2 reduction at the surface ocean after alkalinity addition and (2) the uptake efficiency (ηCO2) after air–sea equilibration is reached. The relative biases of alkalinity versus DIC at the surface affect the Revelle factor and therefore the initial pCO2 reduction after alkalinity addition. The global mean surface alkalinity bias relative to GLODAPv2 in the different models ranges from −85 mmol m−3 (−3.6 %) to +50 mmol m−3 (+2.1 %) (mean: −25 mmol m−3 or −1.1 %). For DIC the relative bias ranges from −55 mmol m−3 (−2.6 %) to 53 mmol m−3 (+2.5 %) (mean: −13 mmol m−3 or −0.6 %). All but two of the CMIP6 models evaluated here overestimate the Revelle factor at the surface by up to 3.4 % and thus overestimate the initial pCO2 reduction after alkalinity addition by up to 13 %. The uptake efficiency, ηCO2, then takes into account that a higher Revelle factor and a higher initial pCO2 reduction after alkalinity addition and equilibration mostly compensate for each other, meaning that resulting DIC differences in the models are small (−0.1 % to 1.1 %). The overestimation of the initial pCO2 reduction has to be taken into account when reporting on efficiencies of ocean alkalinity enhancement experiments using CMIP6 models, especially as long as the CO2 equilibrium is not reached.