Polymer-based solid-state batteries (SSBs) have received increasing attentions due to the absence of interfacial problems in sulfide/oxide-type SSBs, but the lower oxidation potential of polymer-based electrolytes greatly limits the application of conventional high-voltage cathode such as LiNi_xCo_yMn_zO₂ (NCM) and lithium-rich NCM. Herein, this study reports on a lithium-free V₂O₅ cathode that enables the applications of polymer-based solid-state electrolyte (SSE) with high energy density due to the microstructured transport channels and suitable operational voltage. Using a synergistic combination of structural inspection and non-destructive X-ray computed tomography (X-CT), it interprets the chemo–mechanical behavior that determines the electrochemical performance of the V₂O₅ cathode. Through detailed kinetic analyses such as differential capacity and galvanostatic intermittent titration technique (GITT), it is elucidated that the hierarchical V₂O₅ constructed through microstructural engineering exhibits smaller electrochemical polarization and faster Li-ion diffusion rates in polymer-based SSBs than those in the liquid lithium batteries (LLBs). By the hierarchical ion transport channels created by the nanoparticles against each other, superior cycling stability (≈91.7% capacity retention after 100 cycles at 1 C) is achieved at 60  in polyoxyethylene (PEO)-based SSBs. The results highlight the crucial role of microstructure engineering in designing Li-free cathodes for polymer-based SSBs.