Niobium oxide films are promising cathodic electrochromic materials that in certain aspects can compete with the more frequently studied films. The films reported here were prepared using the sol‐gel route from a precursor. The electrochromic properties were pronounced for crystalline films heat‐treated at 500°C exhibiting transmittance changes between the colored and bleached states of 60% in the ultraviolet (UV) and 80% in the visible and near‐infrared spectral regions. The reversibility of electrochromic changes of thick niobium oxide films ( d > 250 nm) was enhanced by lithiation.