Triboelectric nanogenerators (TENG) are a possible power source for wearable electronics, but the conventional electrode materials for TENG are metals such as Cu and Al that are easy to be oxidized or corroded in some harsh environments. In this paper, metal electrode material is replaced by an electrical conducting polymer, polypyrrole (PPy), for the first time. Moreover, by utilizing PPy with micro/nanostructured surface as the triboelectric layer, the charge density generated is significantly improved, more superior to that of TENG with metals as the triboelectric layer. As this polymer-based TENG is further integrated with PPy-based supercapacitors, an all-plastic-materials based self-charging power system is built to provide sustainable power with excellent long cycling life. Since the environmental friendly materials are adopted and the facile electrochemical deposition technique is applied, the new self-charging power system can be a practical and low cost power solution for many applications.