A series of high refractive index of α,ω-vinyl silyl terminated polydimethylsiloxane-co-polydiphenylsiloxane was synthesized by the equilibration ring opening – anionic polymerization of cyclic organo-siloxane oligomers in the present of 1,3-divinyltetramethyldisiloxane as terminating agent. Structural modifications were characterized by use of FTIR, H-NMR, and solution viscosity. UV-visible spectroscopy was analyzed which reveal a good transmittance in the region 400 – 750 nm radiation for all polysiloxanes.The presence of diphenylsiloxane unit results in a linear increase of the refractive index of the resin. These features favor good application as encapsulant for high brightness LED (HBLED) packaging.