The reaction between [(Ph2Si)2O3]4[Al(OH)]4(1) or [(Ph2Si)2O3]4[Al(OLi)]4(2) with sodium ethoxide, or lithium hydroxide in presence of CuI·H2O leads to the formation of new alumopolysiloxane compounds. Indeed, transformations of1under the partial incorporation of the reactants are found giving rise to new heteroleptic inorganic macrocycles. The molecular structure of [(Ph2Si)2O3]4[Al(ONa)]2[Al(OH)(NaOEt)]2·2Et2O (3) and [(Ph2Si)2O3]4[Al(OLi)]2[Al(OH)(LiOH)]2·2Et2O·2THF (4) have been determined by single-X-ray diffraction analysis. Both alumosiloxanes3and4are constituted by a twelve-membered ring.