The dendrite growth and volume expansion of the Li metal anode, as well as the LiPSs “shuttle effect” and slow conversion kinetics of the S cathode, have severely hampered the large‐scale development of LSBs. Herein, a simple hydrothermal method is employed to synthesize rod‐like AgVO3, which is then used as the Li metal anode current collector and the separator modification, respectively. As the Li metal anode current collector, AgVO3 has a strong Li affinity, which can lower Li nucleation overpotential and guide uniform deposition of Li metal. The AgVO3‐modified separator can accelerate the redox kinetics of LiPSs and achieve the anchoring of LiPSs. The results of DFT calculation and experiments reveal that the AgVO3 enable the Ag horizontal d orbitals (dxy/dx2‐y2) to hybridize with the S p orbital to form additional σ/σ* and π/π*. The activation of horizontal d orbitals can increase LiPSs anchoring ability, reduce the reaction barrier, and accelerate LiPSs transformation. Hence, the LSBs assembled with the Li@AgVO3 anode and AgVO3 modified separator show excellent cycle performance. This work gives a novel idea for the application of high catalytic performance materials represented by AgVO3, and its unique catalytic performance can successfully achieve LSBs with high performance.