The gold films (the average thickness is 6.4 nm) coated on the surface of poly (ether-ether-ketone) (PEEK) film and PEEK fiber by the magnetron sputtering system were prepared. Transient electrothermal technique (TET) was used to acquire thermal and electrical conductivitiy of the gold films. The thermal conductivity, electrical conductivity and the Lorenz number of the gold film coated on PEEK film is 283.97 W·m-1·K-1, 2.46×107 Ω-1·m-1 and 3.49×10-8 W·Ω·K-2, respectively. The thermal conductivity, electrical conductivity and the Lorenz number of the gold film coated on PEEK fiber is 81.11 W·m-1·K-1, 1.20×107 Ω-1·m-1 and 2.17×10-8 W·Ω·K-2, respectively. It can be seen that the thermal conductivity, electrical conductivity and Lorenz number of the gold films coated on the different substrate materials are different. The difference is attributed to the facts that the different substrate materials can affect the grain size of the gold film and the flatness of the interface between the substrate and the gold film. The smaller the grain size is, the smaller the electron conductivity and thermal conductivity is. The worse the interface roughness is, the smaller the phonon thermal conductivity is.