We demonstrate a new way to improve the efficiency of the charge transfer in a triboelectric nanogenerator (TENG) based on contact-separation mode. The low efficiency may be due to the non-uniform surface charging which may be originated from the non-uniform surface potential at the surface and the rigid contact surface. It can be improved by fabricating highly stretchable electron donating layer which is composed of PDMS conducting films embedded in Ag nanowires. On the Ag nanowires, the Au nanoparticles capped by DMAP are then decorated on the nanowires. The molecules are found to be positioned to be perpendicular to the gold surface via the positively charged exocyclic nitrogen. This will create the strong local electric field within a few nanometer of the Au particle surface, enhancing the transfer of electron from the Au surface when the PDMS is contacted. Furthermore, it increases the surface potential, increasing the work function difference between Au and PDMS, thereby, the charge density on both surface. The designed TENG gave an output performance up to 80 V and 86 μA, and 2.5 mW, 2~2.5 times enhancement compared with the conventional TENG. Through our researches, not only the energy harvesting will be improved to technologies and products that reach people’s daily life, but also the development of the stretchable devices that will be largely propelled.