Low-temperature techniques for doping of Cu interconnects based on interfacially-assisted thermal diffusion are provided. In one aspect, a method of forming doped copper interconnects includes the steps of: patterning at least one trench in a dielectric material; forming a barrier layer lining the trench; forming a metal liner on the barrier layer; depositing a seed layer on the metal liner; plating a Cu fill into the trench to form Cu interconnects; removing a portion of a Cu overburden to access an interface between the metal liner and the Cu fill; depositing a dopant layer; and diffusing a dopant(s) from the dopant layer along the interface to form a Cu interconnect doping layer between the metal liner and the Cu fill. Alternatively, the overburden and the barrier layer/metal liner can be completely removed, and the dopant layer deposited selectively on the Cu fill. An interconnect structure is also provided.