Thermal management is significant to maintain the reliability and durability of electronic devices. Heat can be dissipated using thermal interface materials (TIMs) comprised of thermally conductive polymers and fillers. Furthermore, it is important to enhance the thermal conductivity of TIMs through the formation of a heat transfer pathway. This paper reports a polymer composite containing vertically aligned electrochemically exfoliated graphite (EEG). We modify the EEG via edge selective oxidation to decorate the surface with iron oxides and enhance the dispersibility of EEG in polymer resin. During the heat treatment and curing process, a magnetic field is applied to the polymer composites to align the iron oxide decorated EEG. The resulting polymer composite containing 25 wt% of filler has a remarkable thermal conductivity of 1.10 W m− 1 K− 1 after magnetic orientation. These results demonstrate that TIM can be designed with a small amount of filler by magnetic alignment to form an efficient heat transfer pathway.