Two routes to obtain well-ordered Langmuir-Blodgett (LB) films from polymeric metal complexes were evaluated. Due to the chemical and structural diversity of metal complexes the methods have to work with different complexes. Two different ways have been investigated. Firstly, ligand functions were introduced in amphiphilic maleic acid copolymers. To these polymers a lot of coordinatively unsaturated precursor complexes may be attached. The complexes’ geometries have a strong influence on their orientation in the multilayers. Secondly, bifunctional amphiphilic ligands on the basis of methylene-bis-salicylidene hexadecylamine are able to form linear coordination polymers with bivalent metal cations. As in the first case it has been proved to be the best way to form the polymeric metal complexes directly at the water surface in an interfacial reaction between the dissolved metal component and the spread amphiphilic ligand or polymer, respectively. The formation of the polymeric complexes was studied by appropriate monolayer experiments and LB layers were investigated by spectroscopic methods.