The interaction of lithium atoms into amorphous tungsten oxide films deposited by thermal evaporation, sputtering and sol-gel synthesis is studied spectroscopically. The mechanism of insertion of lithium into the film depends on the amount and the bonding state of water to the tungsten oxide network. Thermally evaporated tungsten oxide film contains water bonded chemically in the form of a hydrogen tungsten bronze which facilitates the accommodation of a high number of lithium atoms. In the sputtered film, water is physisorbed and the lithiation is incomplete. Tungsten oxide films prepared by sol-gel synthesis have structural water molecules directly involved in the lithiation process. The formation of lithium tungstate independent of the preparation method is demonstrated.