Nanocrystalline W oxide films were produced by advanced reactive gas deposition. The material consisted of ∼6 nm diameter tetragonal crystallites, as found from x-ray diffraction and electron microscopy. Optoelectrochemical measurements demonstrated electrochromism upon Li+ intercalation/deintercalation, and infrared absorption spectroscopy gave clear evidence for longitudinal and transversal optical modes being modified following the lithiation. Our data were consistent with ionic transport predominantly in disordered grain boundaries and intercrystalline regions and with electrochromism being associated with small polaron formation. © 2001 American Institute of Physics.