Monolayer morphology of some amphiphilic europium(III) complexes with different long chains and head groups has been investigated and directly observed at the air/water interface by Brewster angle microscopy. The domain structure and collapse processes for the monolayers of Eu complexes mere closely related to the length and numbers of long chains and to the hydrophilicity of head groups of these complexes. Monolayer assembles of these complexes were fabricated by the LB method and a horizontal lifting technique. The emissions from both the higher excited singlet state D-5(1) Of the europium ion and the symmetric forbidden transition D-5(0)-->F-7(0) are enhanced in LB films in comparison with those in solutions and solid powders. Stronger effects on europium ion emissions were revealed for the complexes with asymmetric beta-diketonate ligands in LB films than for the complexes with symmetric ones. It is suggested that the nonradiative energy transfer D-5(1)-->D-5(0) of europium complexes is decreased and also the closely packed arrangement has some effects on the splitting of Eu3+ ground states in LB films, especially for those with low symmetry of the ligands around central ions.