This study aims to explore the changes in a microalgal biokarst system as a potential carbon sink system in response to pH changes. The bidirectional isotope labeling method and mass balance calculation were adopted in a simulated biokarst environment with a series of set pH conditions and three microalgal species. Three key processes of the microalgal biokarst system, including calcite dissolution, CaCO3 reprecipitation, and inorganic carbon assimilation by microalgae, were completely quantitatively described. The combined effects of chemical dissolution and species-specific biodissolution caused a decrease in overall dissolution rate when the pH increased from 7 to 9. CaCO3 reprecipitation and the utilization of dissolved inorganic carbon originating from calcite dissolution decreased when the pH increased from 7 to 9. The three processes exhibited different effects in changing the CO2 atmosphere. The amount of photosynthetic carbon sink was larger at high pH values than at low pH values. However, the CO2 sequestration related to the biokarst process (biokarst carbon sink) increased with decreasing pH. Overall, the total amount of sequestered CO2 produced by the biokarst system (CaCO3-CO2-microalgae) shows a minimum at a specific pH then increases with decreasing pH. Therefore, various processes and carbon sinks in the biokarst system are sensitive to pH changes, and biokarst processes play an important negative feedback role in the release of CO2 by acidification. The results also suggest that the carbon sink associated with carbonate weathering cannot be neglected when considering the global carbon cycle on the scale of thousands of years (<3 ka).