A new alkoxide-based sol containing lithium isopropoxide, vanadylisopropoxide, di-n-butyl-phosphate, acetic-acid and polyvinylpyrrolidone, was used for the synthesis of monoclinic α-Li3V2(PO4)3/C composites by sol-gel and electrospinning techniques. The precursor mixture was highly soluble in organic solvents and thereby suitable for different synthesis techniques like sol-gel electrospinning or conventional sol-gel synthesis, to generate α-Li3V2(PO4)3/C nanocomposites with zero- and one-dimensionality. Electrospinning resulted in well-defined nanofibers and conventional sol-gel synthesis in polydisperse, isotropic nanoparticles. Phase composition and morphology in the composite nanostructures was examined by XRD, TGA, FT-IR, Raman, SEM and HR-TEM analysis. Comparative constant-current and cyclovoltammetric measurements of α-Li3V2(PO4)3/C composite applied as conventional film electrodes (nanoparticles and nanofibers) and self-supporting nanofiber electrodes revealed the influence of electrode texturing on the electrochemical performances. The nanofibrous self-supported electrodes showed superior cycling stability giving an initial discharge capacity of 124mAhg−1 at 0.2°C with retention of 95% after 50 cycles with rate variation in a voltage range of 3–4.3V.