In this work, we showed that metal salts were easily deposited as aggregates (e.g., ultrathin planar microcrystals) on the surface of TiO 2- gel films in the absence of ion-exchange sites. In contrast, metal ions were efficiently incorporated into ultrathin TiO 2- gel films, when ion-exchange sites were created using Mg ( O - Et )2 as template. A variety of metal ions, including those of main group, transition, and lanthanide elements were successfully doped into TiO 2 thin films by the current approach. Probable distribution of the ion-exchange site in the film interior was discussed.