An effective method for preparing tungsten carbide coating on diamond surfaces was proposed to improve the interface bonding between diamond and copper. The WC coating was formed on the diamond surfaces with a reaction medium of WO3 in mixed molten NaCl–KCl salts and the copper–diamond composites were obtained by vacuum pressure infiltration of WC-coated diamond particles with pure copper. The microstructure of interface bonding between diamond and copper was discussed. Thermal conductivity and thermal expansion behavior of the obtained copper–diamond composites were investigated. Results indicated that the thermal conductivity of as-fabricated composite reached 658 W m− 1 K− 1. Significant reduction in coefficient of thermal expansion of the composite compared with that of pure copper was obtained.