The molecular alumosiloxane (Ph
2
SiO)
8
(AlO(OH))
4
·4Et
2
O (
1
) reacts with 4,4′-bipyridine and azobipyridines (4,4′-azobipyridine and 3,3′-azobipyridine) to form polymer adducts. The acidic hydroxygroups of
1
interfere with the pyridine-nitrogen atoms to form O···H···N hydrogen bridges which are the source of one- and two-dimensional networks. As reaction products we have characterized (Ph
2
SiO)
8
[AlO(OH)]
4
·2p-(C
5
H
4
N)
2
(
2
), (Ph
2
SiO)
8
[AlO(OH)]
4
·1.5p-(C
5
H
4
N)
2
N
2
·C
4
H
8
O (
3
) and (Ph
2
SiO)
8
[AlO(OH)]
4
·2m-(C
5
H
4
N)
2
N
2
(
4
). In the crystal structure of
2
, the supramolecular adduct forms a one-dimensional connection. In
3
and
4
two-dimensional connections are formed. The azobipyridine ligands in solution show cis-trans-isomerisation by application of light even in the supramolecular state (as base adducts of (Ph
2
SiO)
8
[AlO(OH)]
4
).