Here, we demonstrate the fabrication of a Cu-graphene heterostructure interconnect by the direct synthesis of graphene on a Cu interconnect with an enhanced performance. Multilayer graphene films were synthesized on Cu interconnect patterns using a liquid benzene or pyridine source at 400 °C by atmospheric pressure chemical vapor deposition (APCVD). The graphene-capped Cu interconnects showed lower resistivity, higher breakdown current density, and improved reliability compared with those of pure Cu interconnects. In addition, an increase in the carrier density of graphene by doping drastically enhanced the reliability of the graphene-capped interconnect with a mean time to failure of >10⁶ s at 100 °C under a continuous DC stress of 3 MA cm⁻². Furthermore, the graphene-capped Cu heterostructure exhibited enhanced electrical properties and reliability even if it was a damascene-patterned structure, which indicates compatibility with practical applications such as next-generation interconnect materials in CMOS back-end-of-line (BEOL).