CO2 capture and storage (CCS) is a promising approach for significantly reducing CO2 emission from industrial ends and mitigating global warming in the coming decades. Given that most of the subsurface formations are biological active environments, the deep microbial biosphere plays an important role in governing the fate and sequestration efficiency of injected CO2. While substantial researches have explored the initial states and microbial shifts following CO2 injection, there remains a notable gap in studies that systematically examine the interactions between deep microbial biospheres and geologically injected CO2. Such understanding is essential for elucidating mechanisms and extents of geochemical CO2 evolution under the subsurface microbial mediation. This paper comprehensively examines recent findings about impacts of CO2 injection on deep microbial biosphere, and discusses microbial responses that are pivotal in determining the fate of the injected CO2. Initially, the review addresses the influence of elevated CO2 on geological chemistry, including pH, ionic strength, redox state and free energy distribution. Subsequently, it delves into the adverse effects of CO2 on microbial growth, cell integrity, endospore generation, metabolism and community dynamics. Lastly, the review emphasizes key microbial activities that potentially facilitate in situ CO2 immobilization, including CO2 mineralization, methanogenesis and conversion to other valued chemicals. The objective of this review is to elucidate how elevated CO2 levels affect geological microbiology, and how microbial responses impact the fate and speciation of CO2 in storage sites, and to provide insights for optimizing future CO2 storage strategies in geological formations.