In this work, we developed an eco-friendly and facile microvia filling method by using printing and sintering of Cu-Ag core-shell nano-microparticles (Cu@Ag NMPs). Through a chemical reduction reaction in a modified silver ammonia solution with L-His complexing agent, Cu@Ag NMPs with compact and uniform Ag shells, excellent sphericity and oxidation resistance were synthesized. The as-synthesized Cu@Ag NMPs show superior microvia filling properties to Cu nanoparticles (NPs), Ag NPs, and Cu NMPs. By developing a dense refill method, the porosity of the sintered particles within the microvias was significantly reduced from ~30% to ~10%, and the electrical conductivity is increased about twenty-fold. Combing the Cu@Ag NMPs and the dense refill method, the microvias could obtain resistivities as low as 7.0 and 6.3 μΩ·cm under the sintering temperatures of 220 °C and 260 °C, respectively. The material and method in this study possess great potentials in advanced electronic applications.