The W/Cu binary system is characterized by its mutual insolubility and excellent wettability, making W/Cu composite materials ideal for managing thermal and electrical properties in electronic components. To optimize material properties, control over the microstructure is crucial, and nanocomposites with uniform dispersion offer significant advantages. In this study, W/Cu composite nanoparticles were synthesized by feeding a blended feedstock of tungsten trioxide (WO₃) micro-powder and cupric oxide (CuO) micro-powder into a reactive radio frequency (RF) argon–hydrogen thermal plasma system. Cu-coated W nanocomposite particles were obtained through the vaporization, reduction, and condensation processes. The resulting nanocomposite particles were composed of body-centered cubic (BCC) α-W, A15 β-W, and face-centered cubic (FCC) Cu phases, with a chemical composition closely matching theoretical calculations. The phase evolution and morphological changes of the synthesized particles were analyzed as a function of heat treatment temperatures up to 1000 °C in a reducing atmosphere. Up to 600 °C, the phase composition and morphology remained stable. At 800 °C, localized diffusion and coalescence of Cu led to the formation of particulate Cu, and a significant phase transformation from metastable β-W to α-W was observed. Additionally, extensive Cu segregation due to long-range diffusion resulted in distinct Cu-rich and Cu-depleted regions. In these regions, notable sintering of W particles and the complete disappearance of β-W occurred. The results showed that the temperature-dependent redistribution of Cu plays a crucial role in the phase transformation of W and the morphology of W/Cu composite particles.