<p>This approach enables the successful assembly of three-dimensional hierarchical microspheres, where lanthanide metal cations (LMCs, LMCs = lanthanum, cerium, neodymium, samarium) occupying the V sites created through a thermal quenching-modified strategy. As anticipated, these modifications also introduce additional pseudo-capacitance, significantly improving the kinetics of zinc–ion storage and diffusion. Furthermore, among the selected lanthanide cations, a smaller ionic radius correlates with a larger interlayer spacing, which in turn leads to enhanced capacity performance. Unquestionably, the Zn//Nd(III)–VO battery achieves an impressive capacity of 634.06&#xa0;mA&#xa0;h&#xa0;g⁻¹, along with a remarkable power density of 782.56 W kg⁻¹ and a high energy density of 495.62 W h kg⁻¹ at 0.1 A g⁻¹. This performance surpasses that of the vast majority of previously reported similar works. The material demonstrates excellent cyclic stability, maintaining 91% of its capacity over 3000 cycles at a high current density of 10 A g⁻¹. The innovative and straightforward design and construction methods for high-performance aqueous ZIBs are supported by experimental and characterization results. This insightful research not only provides a foundational understanding but also serves as a catalyst for further exploration, potentially extending to other research methodologies and advancing practical applications in the field. Structural characterization and subsequent electrochemical performance tests revealed that the stabilized lattice oxygen, the pinning effect of LMCs, and the elongation of apical “V = O” and “V–O” bonds collectively enhance the intrinsic electronic conductivity of V₂O₅.</p>