The deep eastern edge of the Ordos Basin is rich in coalbed methane, presenting great potential for development. Meanwhile, CO₂ imbibition is an important method to increase production. To study the CO₂-water-rock interactions and microstructural damage characteristics before and after supercritical carbon dioxide immersion in deep coal rocks, CO₂ imbibition experiments were conducted on these rocks by using nuclear magnetic resonance and scanning electron microscopy imaging techniques. The results showed that CO₂ imbibition leads to pore dilatation and reveals the key role of coal rock anisotropy on imbibition efficiency under different physicochemical conditions. Specifically, the immersion of CO₂ produces cracks due to the brittle action of the coal rock, as well as calcite dissolution that exacerbates crack production and expansion. Due to adsorption of CO₂, part of the coal rock becomes swollen, which leads to detachment and changed the physical properties and surface characteristics of the coal rock.