Intercalation of inorganic materials into organized organic assemblies provides possibility for developing new functional materials possessing superior physicochemical properties. A composite material consisting of Prussian blue intercalated into photo-responsive organic molecules (azobenzene-containing multibilayer vesicles) was made. Photoisomerization of the film was attended with geometrically confined structural change within the vesicles as reflefted by changes in dipole moment and electrostatic field. It was consequently possible to control the magnetic properties of the new material by photo-illumination, as well as magnetic properties of photo-isomerizable nano-film containing iron oxide particle by photoillumination at room temperature.