To solve poor engineering performance of copper-tungsten alloys operated at high temperatures, 3D network tungsten frameworks were prepared using a selective laser melting (SLM) process, and then copper was melted and diffused into these tungsten network structures to form copper matrix composites with different copper contents (i.e., Cu-10vol%W and Cu-30vol%W). Their mechanical/electrical properties and arc ablation performance were characterized. Results showed the obtained CuW composites were dense with good interfacial bonding, and the connected Cu phases formed a heat conduction channel and improved electrical and thermal conductivities of the composites. Electrical conductivities of Cu-30W and Cu-10W composites were 44.7% and 80.3% IACS, and their thermal conductivities at 25 °C were 247.5 and 375.4W/(m·K), respectively. The W-skeleton grid structure in the composites showed enhanced effects on impact toughness and anti-friction/wear resistance. Tensile strengths of Cu-30W and Cu-10W composites measured at 300 °C were 95 MPa and 135 MPa, and their impact toughness values were 11.25 and 15.25 J/cm2 , respectively. For the arc ablation performance, the copper phase of CuW composite was identified as the key influencing phase, whereas the W skeleton effectively hindered the spread of arc spots, inhibited quick melting of copper phases, and played effective support and protection functions.