In this work the nanocomposite of vanadium oxide with conducting polymer poly(3,4-ethylenedioxythiophene) (VO@PEDOT) was obtained by microwave-assisted hydrothermal synthesis. The detailed study of its structural and electrochemical properties as cathode of aqueous zinc-ion battery was performed by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction analysis, X-ray photoelectron spectroscopy, thermogravimetric analysis, cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The initial VO@PEDOT composite has layered nanosheets structure with thickness of about 30–80 nm, which are assembled into wavy agglomerated thicker layers of up to 0.3–0.6 μm. The phase composition of the samples was determined by XRD analysis which confirmed lamellar structure of vanadium oxide V ₁₀O ₂₄∙12H ₂O with interlayer distance of about 13.6 Å. The VO@PEDOT composite demonstrates excellent electrochemical performance, reaching specific capacities of up to 390 mA∙h∙g ⁻¹ at 0.3 A∙g ⁻¹. Moreover, the electrodes retain specific capacity of 100 mA∙h∙g ⁻¹ at a high current density of 20 A∙g ⁻¹. The phase transformations of VO@PEDOT electrodes during the cycling were studied at different degrees of charge/discharge by using ex situ XRD measurements. The results of ex situ XRD allow us to conclude that the reversible zinc ion intercalation occurs in stable zinc pyrovanadate structures formed during discharge.