A third generation poly(propylene imine) dendrimer functionalized with oligo(phenylene vinylene) groups is used as a stabilizing agent in the fabrication of CdS nanoparticles. The solvent-dependent conformational behavior of this electroactive dendrimer is used to generate various organic-inorganic semiconductor composites. In chloroform solution, CdS spherical nanoparticles are formed, whereas in a chloroform/ methanol mixture (6:1, v/v) platelike structures evolve. At the air-water interface, nanoparticulate films with a leaf-nerve-like organization of nanoparticles are formed, whereas vesicles generated in aqueous media become overgrown with CdS.