The study reports a microwave-assisted hydrothermal production of V2O5-based composites modified with conductive polymer – poly(3,4-ethylenedioxythiophene) (PEDOT) as a cathode material for Li-ion batteries with enhanced electrochemical stability. During in-situ oxidative polymerization of EDOT in the presence of V2O5 powder partial reduction of V5+ to V4+ with induced oxygen vacancies, combined with recrystallization into mixed valence V10O24⋅12H2O with layered morphology is observed. A gradual enhancement of recrystallization intensity was achieved with increasing synthesis temperature (140 °C–180 °C) and EDOT/V2O5 ratio (0.25–0.5). The resulting composite with the highest amount of V4+, oxygen vacancies, and incorporated PEDOT demonstrates a charge capacity of 185 mAh⋅g−1 with a superior cycling performance (107 % capacity retention after 100 cycles at 0.02 A⋅g−1). This outstanding stability is provided by the layered structure that enables reversible (de)intercalation of Li+ over a wide voltage range (1.5–4.0 V).