The insertion reaction of commercially available polycarbonate (PC) and polyarylate (PAR) with unsaturated epoxides produced new macromonomers grafted with many unsaturated group pendants in the middle of the polymer chain in fair to good yields. The insertion reaction readily occurred not only in solvents but also in solid PC. The unsaturated group was hydrosilylated with triethoxysilane to produce triethoxysilyl group pendant PC and PAR, which are expected to be useful for sol-gel precursors for organic-in organic hybrid materials, in good yields. (C) 2008 Wiley Periodicals, Inc.