Al/expanded graphite was successfully synthesized through a facile method including ultrasonic and heat treatment. In the well-designed three dimensional structure, expanded graphite(EG) works as a conductive matrix to support coated Al particles. The effects of the fabrication parameters on the microstructures and thermal conductivities of these composites were investigated. As a result, it was found that composites with graphite volume fraction of 17.4-69.4% sintered at 600 °C/45 MPa exhibit in-plane thermal conductivities of 380-940 W/mK, over 90 % of the predictions by rule of mixture. According to the non-destructive analysis results, the synergistic enhancement was caused by the formation of efficient thermally conductive pathways due to the hybrid of the differently sized EG. The structure integrates the advantages of expanded graphite as a conductive support, preserving the electrode activity and integrity and improving the electrochemical performance.