The association of nanoparticles with polymer blends offers significant features beyond the advantages of polymer composites prepared by single homopolymer. Since the blends undergo phase separation due to incompatibility of the constituent polymers into various internal structures, the particles can be segregated into one of the phases. Different location of the particles allows to develop novel microstructures; and thus, control over physical properties. In this study, Ag nanoparticles were prepared by reduction of AgNO3 via NaBH4. The particles were capped by cetyl ammonium bromide (CTAB) and were mixed with equimass blend of polystyrene (PS) and poly(methyl methacrylate) (PMMA) in tetrahydrofurane (THF). The solid content of blend solution was fixed at 2.5% w/v. The concentration of the particles with respect to polymer blend was at 0.7 wt %. The composite film was cast on glass slide. Surface feature of the composite films was examined by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The surface of blend film without particles shows spherical pits with a size of 4.5 μm and rich in terms of PMMA. When particle size was small (diameter is around 20 nm), they preferentially located at the interface of the domains. The large particles with a diameter of 90 nm were found to locate in PMMA phase. Upon annealing of the composite film at 165 ˚C for 3 days, the particles move to the PS domains independent of the particle size and merely PS loaded composite is achieved.