Abstract1,4‐Bis(vinyldiphenylsilyl)benzene (I) has been prepared and copolymerized by Pt‐catalyzed hydrosilylation with 1,9‐dihydridodecamethylpentasiloxane (II), 3,5,7‐tris(3′,3′,3′‐trifluoropropyl)‐1,1,3,5,7,9,9‐heptamethylpentasiloxane (III) and two different α,ω‐bis(hydrido)polydimethylsiloxanes (PDMS). The monomers and polymers were fully characterized by IR, UV, 1H, 13C, 19F, and 29Si‐NMR spectroscopy. The starting PDMS polymers and the product copolymers were further characterized by GPC, DSC, and TGA. The polymers showed thermal transitions characteristic to thermoplastic elastomers. The 1,4‐bis(ethyldiphenylsilyl)benzene moieties displayed melting transitions above room temperature while copolymer glass transition temperatures were below room temperature. Fluorescence spectra and quantum efficiencies of I and copolymers have been determined. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4825–4831, 2006