Manufacturing of flexible electrochromic (EC) devices requires the use of low-temperature films for deposition on electronically conductive foils. With this aim, low-temperature V-oxide films were spin-coated from a dispersion prepared by milling of crystalline V2O5 powder in vanadium(V) tri-n-propoxide oxide/isopropanol sol as dispersant. TEM images showed that the milling procedure enables the introduction of some V2O5 nanocrystallites into the matrix of the V-oxide pigmented film prepared at 150 °C. The electrochromic properties were analyzed using in situ UV–visible absorbance spectroelectrochemistry. The low transmittance values of as-prepared pigmented films revealed the presence of a greater amount of reduced V4+ centers compared to the crystalline sol-gel V2O5 model films. Significant bleaching of pigmented V-oxide films occurred during subsequent 521 cycles in the safe potential range. Three different types of vibrational spectroscopies were applied to examine the powdered V-oxide film, and the results were compared to the band changes for the sol-gel crystalline V2O5 films. For initial films, the modes in the IR reflection-absorption spectra were systematically shifted to higher wavenumbers with regard to the modes in the IR absorbance spectra. Both IR techniques confirmed the reversible shift of the vanadyl V-OA band to lower frequencies and the disappearance of the bridging V-OB-V mode upon intercalation. Raman spectra showed the appearance of two vanadyl stretching modes at 986 and 961 cm−1 that occurred simultaneously with the decrease in the intensity of the bands in the 750–400 cm−1 spectral region. After the deintercalation, the Raman spectra of the low-temperature films showed broad bands that remained after the second bleaching. Finally, a flexible NiO1-x/ormolyte/V-oxide EC device was constructed. The device was composed of two different pigmented films and demonstrated the practical applicability of the low-temperature pigmented films. Display omitted •Low-temperature pigmented V-oxide films with nanocrystalites of V2O5 were fabricated.•V4+ was also present in V-oxide films that were bleached during the cycling.•Ex situ IR reflection-absorption, IR absorption and Raman spectroscopy were applied.•Vibrational properties of pigmented V-oxide were compared to those of crystalline V2O5.•A flexible Ni1-xO/ormolyte/V-oxide EC device was fabricated using two types of pigmented films.