The application of Friedel‐Crafts (FC) alkylation reaction to the in situ compatibilization between polystyrene‐grafted nano‐sized TiO2 (PS‐grafted TiO2) and polypropylene (PP) was assessed. The PS‐grafted TiO2 was first prepared via dispersion polymerization of styrene (St) using 3‐(trimethoxysilyl) propyl methacrylate treated nano‐sized TiO2 (MPS‐treated TiO2) as cores, and then dispersed within PP by melt blending with different contents of FC catalyst, AlCl3/St, to give PP/PS‐grafted TiO2 nanocomposites. The dispersion of PS‐grafted TiO2 in PP and interfacial adhesion of PP/PS‐grafted TiO2 nanocomposites were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. The results indicated that the dispersion of PS‐grafted TiO2 in PP could be improved, with an enhancement of interfacial adhesion between TiO2 and PP, by introducing FC catalyst with adequate concentration, which led to a better thermal stability and resistance to ultraviolet (UV) aging of PP/PS‐grafted TiO2 nanocomposites. The effect of FC catalyst on the compatibilization between the PS‐grafted TiO2 and PP was discussed based on FC alkylation reaction mechanism. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009