The foam films of polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-b-PAA-b-PS) doped with Cd(11) or Pb(II) species were fabricated at the planar liquid/liquid interfaces between a DMF/chloroform (v/v: 1/1) solution of the polymer and aqueous solutions containing cadmium acetate or lead acetate at ambient temperature. Optical microscopic observation shows the thin film is uniform on a larger length scale. Transmission electron microscopic (TEM) investigations reveal that the foam films are made up of microcapsules with the size of several hundreds of nanometers to micrometers. The walls of the microcapsules have a layered structure decorating with nanofibers and hollow nanospheres, where numerous inorganic fine nanoparticles are dispersed homogeneously. The film formation is a result of emulsion droplet-templated assembly and adsorption of the formed microcapsules at the planar liquid/liquid interface. Because of the miscibility of DMF with chloroform and water, DMF migrates to the aqueous phase while water migrates to the organic phase across the interface, resulting in the formation of a W/O emulsion, as revealed by optical microscopic observation, freeze fracture transmission electron microscopic (FF-TEM) observation, and dynamic laser scattering (DLS) investigation. The triblock copolymer molecules and the inorganic species adsorb and self-assemble around the emulsion drops, leading to the formation of the composite microcapsules. X-ray photoelectron spectroscopic (XPS) and FTIR spectroscopic results indicate that two kinds of Cd(II) or Pb(II) species, metal oxide or hydroxide, resulting from the hydrolysis of the metal ions and the coordinated metal ions to the carboxyl groups coexist in the formed thin films, which transform to metal sulfide completely after treating with hydrogen sulfide to get metal sulfide nanoparticle-doped polymer thin films.