Triboelectric nanogenerators (TENG) are able to convert mechanical energy into electricity. In this work, a self-powered electrochemical synthesis circle is designed, in which the electrode material of the TENG, polypyrrole (PPy), is prepared by the pulse output of the PPy-based TENG itself. The TENG based on PPy from self-powered synthesis (SPSPPy) presents a competitive performance compared to those made from commercial pulse sources. A supercapacitor that is fabricated from SPSPPy has a far superior performance than that synthesized by the conventional galvanostatic method. Furthermore, a self-charging power system that integrates a TENG and a supercapacitor is demonstrated to drive an electronic device sustainably. Moreover, the polymerization efficiency is optimized in TENG-based electrochemical synthesis because its high voltage can sustain multiple reactors simultaneously. Its upper limit is theoretically analyzed for optimal energy utility, and a maximum number of 39 reactors can be powered experimentally. Hence, TENG is validated as an effective pulse generator for the synthesis of PPy as well as other electrochemical technology, and this work greatly improves the understandings of TENG-based self-powered electrochemical systems.