Tungsten oxide thin films have applications in various energy-related devices owing to their versatile semiconductor properties, which depend on the oxygen content and crystalline state. The concentration of electrons increases with intrinsic defects such as oxygen vacancies, which create new absorption bands that give rise to colored films. Disorders in the crystal structure produce additional changes in the electrical and optical characteristics. Here, WO3−x thin films are prepared on unheated glass substrates by reactive DC sputtering from a pure metal target, using the discharge power and the oxygen-to-argon pressure ratio as control parameters. A transition from amorphous to polycrystalline state is obtained by increasing the sputtering power and adjusting the oxygen content. The surface roughness is higher and the bandgap energy is lower for polycrystalline layers than for amorphous ones. Moreover, the electrical conductivity and sub-bandgap absorption increase as the oxygen content decreases.