In this study, new functionalized polysiloxane material was synthesized. The polysiloxane-based electrooptic material with side-chain charge-transporting functionalities and nonlinear optical chromophores was investigated through a three-step synthetic route. Elementary analysis and NMR spectra indicate that the polymer has a high degree of substitution. Detailed physical properties showed that the polymer has a glass transition of around 91 degrees C, and its photoconductivity and electrooptic coefficient increase with the increasing applied electric field. Photorefractivity of the system has been demonstrated through the asymmetric energy transfer in a two-beam coupling experiment.