In this work, ultra-high molecular weight polyethylene (UHMWPE)/natural flake graphite (NG) polymer composites with the extraordinary high thermal conductivity were prepared by a facile mixed-heating powder method. Morphology observation and X-ray diffraction (XRD) tests revealed that the NG flakes could be more tightly coated on the surface of UHMWPE granules by mixed-heating process and align horizontally (perpendicular to the hot compression direction of composites). Laser flash thermal analyzer (LFA) demonstrated that the thermal conductivity (TC) of composites with 21.6 vol% of NG reached 19.87 W/(m·K) and 10.67 W/(m·K) in the in-plane and through-plane direction, respectively. Application experiment further demonstrated that UHMWPE/NG composites had strong capability to dissipate the heat as heat spreader. The obtained results provided a valuable basis for fabricating high thermal conductive composites which can act as advanced thermal management materials.