W–30Cu composite materials with different concentrations of TiB2 particles ranging from 0 to 2wt.% were prepared by electroless plating with simplified pretreatment and powder metallurgy. The morphologies of W–30Cu composite powders, original TiB2 powders, W–30Cu/TiB2 composite powders were characterized using field emission scanning electron microscopy. X-ray diffraction analysis was used to characterize the phase of W–30Cu/TiB2 composite powders. Relative density, electrical conductivity, and hardness of the W–30Cu/TiB2 composites were examined. Results showed that uniform Cu-coated W composite powders were successfully synthesized by electroless plating with simplified pretreatment. The addition of TiB2 nanoparticles significantly affected the microstructure and properties of W–Cu composite materials. A good combination of the relative density, electrical conductivity, and hardness of the W–30Cu composite materials can be obtained with the incorporation of TiB2 additive at 0.25wt.%.