Aluminum-based silicon carbide (AlSiC) composites with high thermal conductivity were fabricated by post-oxidization of reaction-bonded silicon carbide (RBSiC) preforms in conjunction with vacuum pressure infiltration technology. The study investigated the control of interfacial reactions in conventional sintering and reaction sintering regimes. Conventional sintering introduced a large amount of SiO2, which was detrimental to the thermal conductivity of the AlSiC composite. In contrast, reaction sintering generated β-SiC, which improved the thermal and mechanical properties. An additional post-oxidization process was proposed and applied to the RBSiC preforms to decontaminate the particle interface and prevent the generation of Al4C3. The XRD analysis revealed that the AlSiC composite treated with post-oxidization did not show an Al4C3 signal. Notably, the thermal conductivity of the sample treated with post-oxidization increased by 6.5% compared to the sample that was not treated. The study also analyzed the impact of particle size distribution on volume fraction and thermal properties. The final results showed that the thermal conductivity, coefficient of thermal expansion, bending strength, and bending modulus of AlSiC composites were 237.3 W/m·K, 8.5×10-6/°C, 325 MPa, and 75.9 GPa, respectively.