At the microscopic scale, the competitive adsorption of CO₂ and H₂O alters the interfacial characteristics of rock surfaces, thereby inducing significant deviations between the microscopic wetting properties and macroscopic behaviors, a phenomenon critically impacting unconventional hydrocarbon extraction. Consequently, this paper analyzes the interfacial interactions and microscopic adsorption mechanisms of CO₂ and H₂O on rock surfaces at the molecular level and characterizes the properties of their adsorption layers. Building on this foundation, existing models of competitive adsorption and adsorption energy are summarized, revealing how alterations in interfacial properties affect wettability. Furthermore, the influence of surface energy, surface tension, surface roughness, organic content, and pore structure on the contact angle is discussed, along with the applicability and limitations of contact angle theoretical models. Overall, this paper proposes a method to achieve the accurate characterization of microscopic wetting behavior by incorporating correction coefficients (e.g., adsorption energy, surface roughness) into macroscopic models.