In recent years, the rapid advancement of self‐powered wearable electronic devices has propelled the research focus toward flexible electrodes for single electrode triboelectric nanogenerators (STENG). However, there is currently a lack of reported methods for large‐scale preparation and high‐efficiency molding of these flexible electrodes. In this study, PBAT‐co‐PEG/NaSCN blends‐based ionic conductive thermoplastic elastomer (ICTE) are successfully prepared by initially conducting melt transesterification, followed by melt blending. The STENG, featuring an ICTE electrode, exhibited a remarkable open‐circuit voltage of 50 V, short‐circuit current of 460 nA and charge transfer of 16 nC. With the aid of Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC), the conduction mechanism of ICTE is elucidated. Due to good fluidity and processing performance, bars of ICTE suitable for mechanical properties test could be conveniently prepared via injection molding, which demonstrates the tensile strength and elongation, 13 MPa and 2500%, respectively. A 4 × 4 cm2 STENG fabricated with ICTE electrode could not only have good energy‐harvesting performance but also could be used in a sensor to sense the motion detection. The ICTE, with its simple and environmentally friendly preparation process and high‐efficiency molding, exhibits a promising prospect in the large‐scale preparation and application of flexible STENG.