Ag/Y2O3 has excellent potential to replace Ag/CdO as the environmentally friendly electrical contact material. Using spherical Y2O3 as the starting material, Ag/Y2O3 contacts with a quasi-continuous network structure were successfully fabricated by a low-energy ball milling treatment. The mean size of Y2O3 used ranged from 243 to 980 nm. Due to the differences in the size of Y2O3, Ag/Y2O3 contacts had different primitive microstructures, thereby exhibiting distinctive anti-arc-erosion capabilities. Ag/Y2O3 contact prepared using 243 nm Y2O3 showed the best anti-arc-erosion capability and the most outstanding electrical performance measures, such as low contact resistance, less mass transfer, and no failure up to 105 cycle times. The quasi-continuous network structure formed in the fine-scare was responsible for the excellent electrical performance. The short distance between Y2O3 particles in the network promoted the cathode arc motion, and thus alleviated the localized erosion. The results obtained herein may inspire further attempts to design electrical contacts rationally.