With the increasing demand for flexible piezoelectric sensor components, research on polyvinylidene fluoride (PVDF) based piezoelectric polymers is mounting up. However, the low dipole polarization and disordered polarization direction presented in PVDF hinder further improvement of piezoelectric properties. Here, we constructed an oriented tertiary structure, consisting of molecular chains, crystalline region, and MXene sheets, in MXene/PVDF nanocomposite via a temperature-pressure dual-field regulation method. The highly oriented PVDF molecular chains form approximately 90% of the β phase. In addition, the crystalline region structure with long-range orientation achieves out of plane polarization orientation. The parallel orientation arrangement of MXene effectively enhances the piezoelectric performances of the nanocomposite, and the current output of the device increases by nearly 23 times. This high output device is used to monitor exercise action, exploring the potential applications in wearable electronics.