Amphiphillic ionic metallomesogens were prepared from several polyoxometalate (POM) species: SiW₁₁O₃₉^8-, P₂W₁₇O₆₁^10-, and V₃P₂W₁₅O₅₉^6-.  All compounds were isolated as tetrabutylammonium (⁴Q⁺) salts.  Amphiphilles based on the SiW₁₁O₃₉^8- and P₂W₁₇O₆₁^10- POMs were prepared with the general formulas ⁴Q₄[(RSi)₂OSiW₁₁O₃₉] and ⁴Q₆[(RSi)₂OP₂W₁₇O₆₁] respectively, where R= CH₃(CH₂)₇- (C8), CH₃(CH₂)₁₁- (C12), or CH₃(CH₂)₁₇- (C18).  Amphiphilles of the V₃P₂W₁₅O₅₆^6- POM were prepared with the general formulas ⁴Q₅H[RCONHC(CH₂O)₃V₃P₂W₁₅O₅₉] and ⁴Q₅H[RCO₂C(CH₂O)₃V₃P₂W₁₅O₅₉], where R= CH₃(CH₂)₁₆-, [CH₃(CH₂)₁₅C]₃C-, or C₆H₅.  LB films and multilayers were prepared from dicholormethane solutions of the ⁴Q₄[(RSi)₂OSiW₁₁O₃₉] amphiphilles on an aqueous subphase.  The compression and expansion pressure isotherms indicate that the LB thin films are well ordered for the C8 and C18 compounds and that the length of the hydrocarbon chain does not exert a strong influence on the packing of the amphiphiles.  In addition, the LB thin films show minimal (<3%) change in the surface structure and organization over time.  Multilayers on ZnSe appear to have a z-type supramolecular structure.