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