Poly [2-(9'-acetyl-10'-phenanthrenyl)ethylmethylsiloxane] (I) has been prepared by the activated dihydridocarbonyltris(triphenylphosphine)ruthenium (Ru)-catalyzed regioselective anti-Markovnikov addition of the 10-C-H bond of 9-acetylphenanthrene across the C-C double bonds of poly(vinylmethylsiloxane) (PVMS). This chemical modification of PVMS is highly efficient. The UV absorption, excitation, and emission spectral properties as well as the thermal properties of I have been studied. For comparison, the monomeric model systems tetrakis[2-(9'-acetyl-10'-phenanthrenyl)ethyldimethylsiloxy]silane (II), 2,3,4-tris[2-(9'-acetyl-10'-phenanthrenyl)ethyl-1,1,1,2,3,4,5,5,5-nonamethylpentasiloxane (III), and 9-acetyl-10-[2'-(trimethylsiloxydimethylsilyl)ethyl]phenanthrene (IV) were prepared by Ru-catalyzed reactions of 9-acetylphenanthrene with tetrakis [vinyldimethylsilyloxy]silane, 2,3,4-trivinyl-1,1,1,2,3,4,5,5,5-nonamethylpentasiloxane, and vinylpentamethyldisiloxane, respectively.