Ceramic/polymer composite with a high thermal conductivity is a candidate of insulating materials for electronic packaging. However, traditional polymer composites filled with alumina (Al2O3) powders present limited enhancement in thermal conductivity even at a high loading due to thermal resistance on the filler/filler and filler/matrix interfaces. Herein, a contiguous 3D network of alumina foam (AF) filled with different diameters of Al2O3 microparticles via vacuum-assisted filtration proves to be a promising filler structure for thermal conductivity composites. The fabricated epoxy/AF/Al2O3 composite exhibits a high thermal conductivity of 4.1 W/mK and a significant thermal conductivity enhancement (TCE) of 2097%. Further study reveals a prominent synergistic effect between the 3D interconnected AF and Al2O3 microparticles, which plays a critical role in the formation of thermal percolation networks to promote thermal conductivity dramatically. Meanwhile, compared to previous reports, the composite resulted in a lower coefficient of thermal expansion (CTE) than those of most epoxy-based composites, showing great potential for heat conduction applications in microelectronics. This result paves an effective way of developing epoxy composites with high thermal conductivity in electronic packaging applications.