Li3V2(PO4)3(LVP) stands out as a promising cathode material due to its higher operating voltage and theoretical capacity, effectively addressing continuous demands. At elevated operating voltages, the electrochemical performance of pure LVP is significantly constrained. This study involved the synthesis of multiwalled carbon nanotubes (MWCNTS) -decorated LVP using a hydrothermal-assisted solid-state method. Employing a range of techniques, the crystalline phase, morphology, microstructure, and composition of the resulting materials were examined. The findings from transmission electron microscopy reveal that the crystalline LVP surface is enveloped by an amorphous carbon layer roughly 3–5 nm thick, with the LVP particles linked by carbon. The evaluation of the electrochemical performance of the LVP cathode at a cut-off voltage of 4.2 V was conducted. The performance of the prepared electrodes was evaluated through electrochemical analysis, which indicated that Li3V2(PO4)3coated with multi-walled carbon nanotubes (MWCNTs) exhibited a capacity of 183 mAh g−1at 100 A g−1. Additionally, in situ XRD patterns were obtained throughout the charging and discharging cycles, indicating that the MWCNT coating contributed to the formation of extra active sites and improved electrode stability over extended cycling periods. Nanostructured Li3V2(PO4)3hybrid cathodes enhance electrical conductivity, offer extensive electrode/electrolyte contact surfaces, facilitate the movement of electrons and Li+, and adeptly manage strain during the insertion and extraction of Li+. The recent advancements in the application of 0D (nanoparticles), 1D (nanowires and nanobelts), 2D (nanoplates and nanosheets), and 3D (nanospheres) Li3V2(PO4)3for high-performance lithium-ion batteries emphasise their fabrication methods and distinctive electrochemical characteristics. The results demonstrate that MWCNT-coated Li3V2(PO4)3could function as a cost-efficient, highly stable, and high-performance electrode for Lithium-ion energy storage applications. © 2025 The Authors. Published by Elsevier Ltd.