An emulsion-directed assembly and adsorption approach has been used to fabricate composite films of polystyrene-b-poly(acryl acid)-b-polystyrene (PS-b-PAA-b-PS) and Eu3+ and La3+ ions at the planar liquid/liquid interface of the polymer DMF/chloroform (1:1, v/v) mixed solution (lower phase) and aqueous solutions of the corresponding salts (upper phase). The lower phase gradually transformed to a water-in-oil (W/O) emulsion via spontaneous emulsification due to the "ouzo effect". Polymer molecules and the metal ions assembled around emulsion droplets that adsorbed at the planar liquid/liquid interface at last, resulting in formation of composite films. The film morphologies and structures depend on Ln(3+) ions: polymer/Eu3+ composite films were foam films composed of microcapsules ranging in size from several hundreds of nanometers to micrometers, while polymer/La3+ composite films were composed of hollow spheres several tens of nanometers in size. Fourier transform infrared (FTIR) spectra revealed that the coordination modes of carboxyl groups to Eu3+ and La3+ were bridging bidentate and ionic, respectively, in the two types of composites. These results indicate that stable microcapsules can be fabricated around droplets for polymer/Eu3+ systems, while microcapsules of polymer/La3+ are unstable. This leads to different film morphologies and structures. Compositions of these films were characterized using energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). In addition, foam films of polymer/Eu3+/2,2'-bipyridine (bpy) were fabricated using this approach, and their photoluminescence properties were investigated. (C) 2014 Elsevier Inc. All rights reserved.