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This work presents the measurements of the Kapitza thermal boundary resistance (TBR) between two types of graphene monolayers epitaxially grown on the silicon face of SiC(0001) substrates by chemical vapor deposition. The studied systems consist of a graphene layer either separated from the bulk SiC by a carbon rich interface layer (called buffer layer BL) exhibiting a 6 3 × 6 3 R 30 ° surface reconstruction or quasifreestanding on the substrate, which will be referred to as QFSMG (for the quasifreestanding monolayer of graphene). The equivalent graphene monolayers' thermal resistances (ratio between the layer thickness and its thermal conductivity) and their respective TBR with the SiC substrates were characterized using a high frequency photothermal radiometry technique in order to distinguish the difference between the two interfaces. The results display a larger TBR through the BL compared to a lower one across the QFSMG. It is suggested that beyond generally used models, the presence of electronic coupling between the QFSMG and the SiC may create new channels for heat conduction at the interface. These results give new insights into the thermal transport at the nanoscale using epitaxial graphene monolayers for better usage in heat management applications (e.g., thermal diodes or thermal transistors). [ABSTRACT FROM AUTHOR]