Graphene/poly(ether ether ketone) (m-TRG/PEEK) composites with excellent electrical conductivity were fabricated by hot pressing technique with thermally reduced graphene nanosheets (m-TRG) which were modified by poly(ether sulfone). Moreover, the conductive, thermal, and mechanical properties of PEEK/m-TRG composites were investigated by the precision impedance analyzer, thermal gravimetric analyzer, differential scanning calorimetry, and universal tester, respectively. The electrical conductivity of m-TRG/PEEK composites was greatly improved by incorporating graphene, resulting in a sharp transition from electrical insulator to semiconductor with a low percolation threshold of 0.76 vol.%. A high electrical conductivity of 0.18 S m(-1) was achieved with 3.84 vol.% of m-TRG. The data were compared with those of composites reduced chemically, and the results showed that thermal reduction was an effective method to acquire higher electrical conductive composites. The excellent electrical property should be attributed to the large specific surface area of m-TRG, well dispersion of m-TRG in PEEK matrix, and good compatibility of m-TRG with PEEK matrix, as proven by scanning electron microscope. Besides, m-TRG/PEEK composites also exhibited relatively good thermal and mechanical properties.