Diamond reinforced copper (Cu/diamond) composites were prepared by pressure infiltration for their application in thermal management where both high thermal conductivity and low coefficient of thermal expansion (CTE) are important. They were characterized by the microstructure and thermal properties as a function of boron content, which is used for matrix-alloying to increase the interfacial bonding between the diamond and copper. The obtained composites show high thermal conductivity (>660 W/(m·K)) and low CET (<7.4×10^-6 K^-1) due to the formation of the B₁₃C₂ layer at the diamond-copper interface, which greatly strengthens the interfacial bonding. Thermal property measurements indicate that in the Cu-B/diamond composites, the thermal conductivity and the CTE show a different variation trend as a function of boron content, which is attributed to the thickness and distribution of the interfacial carbide layer. The CTE behavior of the present composites can be well described by Kerner’s model, especially for the composites with 0.5wt% B.