<p>Red phosphorus (RP), one high theoretical specific capacity (2596&#xa0;mAh&#xa0;g⁻¹) anode material, suffers from severe volume expansion and ion transport lag during charge and discharge process. Herein, barium titanate (BTO) nanoparticles with spontaneous polarization effect are introduced into RP-based composites to suppress the volume expansion of RP and accelerate the bulk charge transfer. In situ X-ray diffraction technology and Kelvin probe force microscopy synergistically clarify the stress applied to BTO during the RP alloying reaction can effectively increase the dipole moment of BTO, thereby increasing the ion diffusion coefficient of RP-based anode material by approximately 30%. Through the spontaneous polarization effect of BTO, RP-based anode exhibits ultrafast discharging capability, showing the specific capability of 600&#xa0;mAh&#xa0;g⁻¹ at 10&#xa0;A&#xa0;g⁻¹. Such efficient strategy of utilizing the spontaneous polarization of piezoelectric materials to improve the bulk charge transport provides a forward-looking idea for the design of high-performance alloying anodes.</p> Graphical abstract <p>The stress generated during the red phosphorus (RP) sodiumization process induces the spontaneous polarization of the piezoelectric material BaTiO₃ and effectively increases its dipole moment. Ultimately, the charge transfer behavior and rate performance of the RP anode are significantly improved.</p>