Dynamic hybrid materials based on Müller's porous Keplerate type molybdenum-oxide based nanocapsules are described. The present efforts involve the preparation and properties of hybrid materials formed between lipophilic MCM41-mesoporous or octadecyldimethylsilica with Keplerate type molybdenumoxide based Mo132 nanocapsules – designed by encapsulation into DODA – dimethyldioctadecylammonium cationic surfactants (DODA)40Mo132. In particular, the use of a ‘‘dynamic reversible hydrophobic interface” between (DODA)40Mo132 and lipophilic silica can render the emerging hybrid mesophases self-adaptive. The reversible hydrophobic interactions allow to both capsule and inorganic silica components to mutually (synergistically) adapt their spatial constitution during simultaneous (collective) formation of self-organized hybrid domains. This might provide new insights into the features that control the design of novel complex materials.