The thermoplastic polymer blends of commercial interest generally need a phase compatibilization to reduce the interfacial tension, to stabilize the morphology, and to increment the interfacial adhesion. This work deals with the compatibilization of PP/PS blends by addition of a tailor-made copolymer, which is prepared from the pure homopolymers by a Friedel-Crafts reaction. This addition compatibilization process comes out as an economic alternative applicable to the recycling of mixed plastics from urban and industrial wastes. The influence of compatibilizer concentration and blending time on the emulsifying effect, morphology, and mechanical properties of the resulting blends are analyzed. The compatibilization process effectiveness is assessed through the improvement in phase adhesion, emulsification and ductility of the compatibilized with respect to the physical blends. An increase of three times in ductility is achieved using very low compatibilizer concentrations (0.5-0.7 wt%). No appreciable detriment in yield strength or modulus is observed in these compatibilized blends.