The thermal and tribological properties of silicon composites were improved by choosing polytetrafluoroethylene (PTFE) as a thickener and alumina nitride (AlN) and flake graphite (FG) as thermal conductive additives, producing AlN‐modified, FG‐modified, and AlN/FG‐modified PTFE‐based thermal silicon composites (AlN–PTSC, FG–PTSC, and AlN/FG–PTSC, respectively). Three‐dimensional network‐configuration representative volume element models were built to investigate the thermal properties of these composites by applying a Monte Carlo, controllable, spatial distribution algorithm. The composites’ thermal conductivity and volume resistance were also measured. Tribological tests were conducted using a ball‐on‐disk reciprocating friction and wear tester. Scanning electron microscopy and energy dispersive spectroscopy were used to analyze the morphologies and elements of worn surfaces. The results showed that AlN/FG–PTSC possessed the best thermal properties, which were ascribed to a compact thermal conductive network; thermal conductivity was 88.8% and 44.8% greater than the highest value of AlN–PTSC and FG–PTSC, respectively. The numerical values of thermal conductivity were in a good agreement with experimental results. The optimal electrical tribological properties of AlN/FG–PTSC were ascribed to the functions of thermal and electrical properties combined, which could be helpful in abating the arc erosion on friction contacts. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45263.