Duplex structure Cu-Cr alloys are widely used as contact materials. They are generally designed by increasing the Cr content for the hardness improvement, which, however, leads to the unfavorable rapid increase of the electrical resistivity. The solidification behavior of Cu 100−x Cr x (x = 4.2, 25 and 50 in wt.%) alloys prepared by laser rapid solidification is studied here, and their hardness and electrical conductivity after aging are measured. The results show that the Cu-4.2%Cr alloy has the most desirable combination of hardness and conductive properties after aging in comparison with Cu-25%Cr and Cu-50%Cr alloys. Very importantly, a 50% improvement in hardness is achieved with a simultaneous 70% reduction in electrical resistivity. The reason is mainly attributed to the liquid phase separation occurring in the Cu-4.2%Cr alloy, which introduces a large amount of well-dispersed sub-micron-scale Cr-rich particulates in the Cu-rich matrix.