Copper interconnects in modern integrated circuits require a barrier layer to prevent Cu diffusion into surrounding dielectrics. However, conventional barrier materials like TaN are highly resistive compared to Cu and will occupy a large fraction of the cross-section of ultra-scaled Cu interconnects due to their thickness scaling limits at 2–3 nm, which will significantly increase the Cu line resistance. It is well understood that ultrathin, effective diffusion barriers are required to continue the interconnect scaling. In this study, a new class of two-dimensional (2D) materials, hexagonal boron nitride (h-BN) and molybdenum disulfide (MoS₂), is explored as alternative Cu diffusion barriers. Based on time-dependent dielectric breakdown measurements and scanning transmission electron microscopy imaging coupled with energy dispersive X-ray spectroscopy and electron energy loss spectroscopy characterizations, these 2D materials are shown to be promising barrier solutions for Cu interconnect technology. The predicted lifetime of devices with directly deposited 2D barriers can achieve three orders of magnitude improvement compared to control devices without barriers.