Randomly oriented vanadium dioxide (VO2) nanowires were produced on a glass substrate by spin coating from a cosolvent. SEM studies reveal that highly dense VO2 nanowires were grown at an annealing temperature of 400 degrees C. X-ray diffraction (XRD) provides evidence of the high crystallinity of the VO2 nanowires-embedded VO2 thin films on the glass substrate at 400 degrees C. Characterization by high-resolution transmission electron microscopy (HR-TEM) confirmed the formation of VO2 nanowires. The optical band gap of the nanowires-embedded VO2 thin films was also calculated from the transmittance data to be 2.65-2.70 eV. The growth mechanism of the solution-processed semiconducting VO2 nanowires was proposed based on both solvent selection and annealing temperature. Finally, the solar water splitting ability of the VO2 nanowires-embedded VO2 thin films was demonstrated in a photoelectrochemical cell (PEC).