Diamond/SiC composites were prepared by vacuum silica vapor-phase infiltration of in situ silicon–carbon reaction, and the thermophysical properties of the composites were modulated by controlling diamond graphitizing. The effects of diamond surface state and vacuum silicon infiltration temperature on diamond graphitization were investigated, and the micromorphology, phase composition, and properties of the composites were observed and characterized. The results show that diamond pretreatment can reduce the probability of graphitizing; when the penetration temperature is greater than 1600 °C, the diamond undergoes a graphitizing phase transition and the micro-morphology presents a lamellar shape. The thermal conductivity, density, and flexural strength of the composites increased and then decreased with the increase of penetration temperature in the experimentally designed range of penetration temperature. The variation of thermal expansion coefficients of composites prepared with different penetration temperatures ranged from 0.8 to 3.0 ppm/K when the temperature was between 50 and 400 °C.