AbstractThe impact of carbon fiber (CF) composites sizing with graphene oxide (GO) to form brick‐and‐mortar structures on their mechanical properties and thermal conductivity has not been closely examined. This study systematically investigates the effect of GO sheet size on the interfacial properties and thermal conductivity of CF composites. Three sizes of GO—small (0.11 μm), medium (0.33 μm), and large (0.97 μm)—were used to modify CF surfaces via layer‐by‐layer self‐assembly, forming the brick‐and‐mortar structures. The mechanical properties were assessed through flexural tests, interlaminar shear strength (ILSS) tests and tensile tests, while thermal conductivity was measured using a thermal constant analyzer. The results revealed that medium‐sized GO (GO‐M) significantly enhanced the interfacial strength and toughness of the composites. This improvement is attributed to the orderly arrangement of GO‐M on the CF surface, which enhances stress transfer between the fiber and the matrix. In contrast, small‐sized GO (GO‐S) tended to scatter, resulting in less effective reinforcement, while large‐sized GO (GO‐L) exhibited stacking and agglomeration, limiting its reinforcement effectiveness. However, GO‐L provided the highest thermal conductivity due to the formation of continuous heat conduction pathways. These findings suggest that GO‐M offers a balanced improvement in mechanical properties, whereas GO‐L is more suitable for applications requiring high thermal conductivity. This work underscores the importance of selecting the appropriate GO sheet size to optimize the interfacial properties and thermal conductivity of CF composites, which is crucial for enhancing their performance in high‐end engineering applications, such as aerospace, automotive, and marine industries.Highlights Modification of CF composites by GO‐M sheets significantly improved toughness and strength. GO‐L sheets formed an effective heat transfer channel with the highest thermal conductivity. The study emphasized the critical role of selecting the appropriate GO sheet size to optimize the mechanical and thermal properties of CF composites.