The diamond and tungsten were firstly mixed and compacted into preforms, and then the preforms were infiltrated by liquid copper without pressure to form the W-diamond/copper composites. The effect of tungsten on microstructure, interface and thermal conductivity of the composites was analyzed by means of SEM, XRD and laser flash thermophysical properties analyzer. The results show that with increase of doping content of tungsten, the interfaces between diamond and copper bond better, and the microstructure is more compact. The tungsten is enriched in the surface of diamond and generates WC, W2C and other carbides. With the increasing of doping content, the thermal conductivity of the composites increases at first and decreases later. The maximum value is about 450 W·m-1·K-1. © 2015, Editorial Office of Transactions of Materials and Heat Treatment. All right reserved.