The molecular mechanism of adhesion of two epoxy resins based on diglycidylether of bisphenol A (DGEBA) cured with 4,4'-diaminodiphenyl sulfone (DDS) and 4,4'-diaminodiphenylmethane (DDM) to the carbon fiber (CF) surface is investigated by employing density functional theory (DFT) calculations. The CF surface was modeled by the armchair-edge structure of graphite functionalized with carboxyl (COOH) groups. Two adhesion interfaces were constructed using the CF surface: one with the DGEBA-DDS molecule (CF/DGEBA-DDS interface) and the other with the DGEBA-DDM molecule (CF/DGEBA-DDM interface). The interfacial properties were analyzed by calculating the maximum adhesion stress (Smax) at the interface. The adhesion stress-displacement curve revealed that Smax is 1160.37 MPa, higher for the CF/DGEBA-DDS interface compared to the CF/DGEBA-DDM interface, which is 1060.48 MPa. The energy decomposition analysis showed a similar DFT contribution to adhesion stress for both interfaces, but the dispersion contribution is more significant at the CF/DGEBA-DDS interface. The crystal orbital Hamilton population (COHP) analysis revealed distinct interfacial interactions despite similar DFT contributions. Hydrogen bonding (H-bonding) between the functional groups at both interfaces including feeble OH-π interactions between the benzene rings of epoxy resins and COOH groups on the CF surface were observed. The orbital interaction energies calculated from integrated COHP, i.e., IpCOHP, revealed that the CF/DGEBA-DDS interface has six H-bonding interactions with large absolute IpCOHP values (>1 eV), whereas the CF/DGEBA-DDM interface has five. The interaction between the amine group of the DGEBA-DDM molecule and the CF surface has a large IpCOHP value among all interactions. The sulfone group being at the center of the DDS molecule and its strong surface interaction positioned the DGEBA-DDS molecule closer to the CF surface than the DGEBA-DDM molecule, enhancing dispersion interaction at the CF/DGEBA-DDS interface. Hence, the CF surface exhibits a stronger affinity toward the DGEBA-DDS molecule than the DGEBA-DDM molecule through dispersion interaction.