For the first time, we report the Li-ion storage performance of V10O24.nH2O with LiPF6 based liquid electrolyte (LE) and PDATFSI-60IL based solid-polymer electrolyte (SPE). The LiǁV10O24.nH2O in LE exhibits a reversible capacity of ∼184/83 mAh g−1 at 0.1/5.0 A g−1, respectively, and features good cycling stability (retained 98.78, and 65.53 % after 1000 and 2000 cycles, respectively). In case of solid-state Li-ion battery (ssLiB), the PDATFSI-60IL membrane is utilized as SPE as well as binder for V10O24.nH2O cathode material. The PDATFSI-based SPE effectively provides reliable Li+ conductive galleries, prevents the Li dendrites formation, and provides stable contact between the cathode and current collector. The resultant V10O24.nH2O cathode exhibit a reversible capacity of ∼152 mAh g−1 at 0.1 A g−1, demonstrating good rate performance (≈152/38 mAh g−1 at 0.1/5 A g−1) with considerable cycling stability (≈72 % capacity retention at 500th charge/discharge cycle).