Metal halides, solvent effects, phase transfer catalysts, alkylating agent and reaction times were found to have important roles to complete halogen exchange reactions in "one pot" synthesis, starting from octakis(3-chloropropyl)octasilsesquioxane to obtain more reactive halide compounds: octakis(3-bromopropyl)octasilsesquioxane and octakis(3-iodopropyl)octasilsesquioxane. To confirm the complete halogen exchange, the desired products were characterized by (1)H, (13)C and (29)Si NMR spectroscopy, ESI-MS, elemental analysis and single-crystal X-ray diffraction analysis.