Diamond reinforced silicon carbide matrix composites (diamond/SiC) with high thermal conductivity were prepared by tape casting combined with Si vapor infiltration for thermal management application. The effects of the mixing mode of bimodal diamond particles on the microstructure, thermal and mechanical properties of the composites were analyzed. The results reveal that the thermal conductivity of composites is affected significantly by mixing mode of diamond. In general, when the content of large diamond remains constant, adding a slight amount of small diamond was found to be effective in improving the thermal conductivity of the composite. However, excess small diamonds added will decrease thermal conductivity due to its high interfacial thermal resistance. The maximum thermal conductivity of obtained diamond/SiC is 469 W/(m K) when 38 vol% large diamond and 4 vol% small diamond were added. Such a result can be attributed to the formation of efficient heat transfer channels within the composite and sound interfacial bonding between diamond and SiC phase. Diamond/SiC with high thermal conductivity are expected to be the next generation of electronic packaging substrate.