With the continuous development of technology, flexible wearable electronic devices have received widespread attention. However, flexible substrate materials with high strength and toughness and flexible stretchable electrode materials that can meet practical needs are still full of challenges. Here, we successfully prepared elastomeric substrate materials with high tensile strength (30.95 MPa), high toughness (134.16 MJ/m3), solvent resistance and puncture resistance by modulating the reaction conditions of maleic anhydride and polystyrene-b-polybutadiene-b-polystyrene. Subsequently, the preparation of flexible and stretchable electrodes was achieved by mixing an elastomeric substrate with carbon nanotubes. The capacitive sensor designed and assembled based on this stretchable electrode has fast response characteristics and can be used for human movement detection. Additionally, the triboelectric nanogenerator (TENG) fabricated using this material for the friction layer exhibits a high open-circuit voltage of 848 V along with a short-circuit current of 20 μA. Its excellent stability is evidenced by its ability to withstand up to 10,000 cycles, and it also possesses an impressive power density of 3.8 W/m2. These characteristics provide a solid foundation for advancing research in intelligent sensing technologies and lay the groundwork for its future incorporation into energy-harvesting devices.