In this paper, boron carbide (B4C) ceramics were added to a copper (Cu) base, to improve the mechanical properties and wear resistance of pure copper. The B4C/Cu composites with different B4C contents, were obtained by mechanical mixing and discharge plasma sintering methods. Scanning electron microscopy (SEM), energy spectrum analysis (EDS), and electron probe microanalysis (EPMA) were used, to observe and analyze the microstructures of the B4C/Cu composites. The influences of the B4C content on the hardness, density, conductivity, and wear resistance were also studied. The experimental results show that B4C has an important effect on Cu. With increasing B4C content, both the density and conductivity of the B4C/Cu composites gradually decrease. The hardness of the Cu-15 wt.% B4C composite has the highest value, 86 HBW (Brinell hardness tungsten carbide ball indenter), which is 79.2% higher than that of pure copper. However, when the B4C amount increases to 20 wt.%, the hardness decreases due to the metallic connection being weakened in the material. The Cu-15 wt.% B4C composite has the lowest volume loss, indicating that it has the best wear resistance. Analyses of worn B4C/Cu composite surfaces suggest that deep and narrow grooves, as well as sharp ridges, appear on the worn pure Cu surface, but on the worn Cu-15 wt.% B4C composite surface, the furrows become shallow and few. In particular, ridge formation cannot be found on the worn Cu-15 wt.% B4C composite surface, which represents the enhancement in wear resistance.