In the present work, tungsten powders coated with copper by electroless plating method, and preparation of WCu20 composites by microwave sintering with copper-coated tungsten powder as raw material. The result shows that at the situation of a temperature of 60 °C, pH value of 12–13, with formaldehyde solution (53 ml/L) as reducing agent, iron potassium cyanide solution (0.3 g/L) as stabilizer, tartaric acid potassium sodium (15 g/L) and EDTA-2Na (19 g/L) mixture solution as compound complexing agent, the thickness of surface coating was relatively uniform, which is around 0.6–1.1 μm. The WCu20 composites were fabricated by microwave sintering with copper-coated tungsten powder as raw material shows uniform microstructure distribution, relatively high density. The hardness of the WCu20 composites increased with the temperature. While the temperature of sintering at 1100 °C for 1 h, the density could be up to 15.22 g/cm3, relative density was 97.13%, which shows better properties.