Abstract: | Polymethylphenylsilsesquioxane (PMPSQ–OH) and trimethylsilyl end‐blocked PMPSQ (PMPSQ–EC) were prepared. The thermal decomposition behavior of these polymers was studied by thermogravimetric analysis (TGA) and FT‐Raman spectroscopy. Hydroxyl‐functionalized polystyrene (PS–OH) was also prepared by anionic living polymerization. Thin hybrid films of PMPSQ/PS–OH with various blend ratios were obtained by spin‐coating on freshly cleaned glass. The surface morphology of the hybrid films was investigated by atomic force microscopy (AFM). In 80/20 PMPSQ/PS–OH hybrid film, the PS–OH component produced a very uniformly dispersed phase. This hybrid film contained small domains of PS–OH whose size ranged from 60 to 80 nm. As the content of PS–OH was increased, the domain morphology coarsened and phase inversion took place around 50 wt %. In the phase‐inversed system, the PMPSQ‐rich phase was uniformly distributed in the PS–OH‐rich continuous phase. In addition, temperature‐dependent dielectric properties of PMPSQ/PS–OH hybrids were investigated. Relaxation of the hybrids was observed with an increasing content of the PS–OH component due to the amorphous glass transition behavior of PS–OH. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2801–2812, 2003 |