Intercalation compounds of lithium-aluminium double hydroxide (LADH) [LiAl2(OH)(6)](n)X . pH(2)O, X-[CuEdta](2-), [CoEdta](2-), [NiEdta](2-), [Fe(CN)(6)](3-) were obtained. Thermal decomposition of LADH-intercalates with complexes of transition metals and Edta leads to the dehydration and dehydroxylation of the hydroxide matrix and to the collapse redox process of the complex anion with the appearence of nanoscale metal particles distributed in a dielectric matrix. Photolysis of [LiAl2(OH)(6)](3)[Fe(CN)(6)]. nH(2)O leads to the formation of nanoscale systems containing two-dimensional lithium-aluminium hydroxide packets separated by [Fe(CN)(6)](4-) complexes and [Fe-x(OH)(6-x)]((3+x)-) clusters.