Among the many forms of mesoporous materials, thin films are important for the potential applications of this class of materials. Compared with the powder forms, however, there has been relatively little work done on thin films probably because of the lack of suitable and generalized synthetic mechanisms established. In this account, we will review the issues on mesoporous thin films with emphasis on the necessity of forming films with accessible pores from the film surfaces and on mesoporous thin films with metal oxides other than silica. Various methods that have been tried to utilize mesoporous thin films with accessible pores as templates for the synthesis of nanostructured materials are reviewed with the emphasis on the advantages of the electrochemical deposition technique.