The monomers, (3-cyanopropyl) methylsiloxane cyclics (D4CN) and (3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)propyl) methylsiloxane cyclics (D4TEG) were prepared by a hydrosilylation reaction of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) with allyl cyanide and tri(ethylene glycol) methyl allyl ether (allyl TEG), respectively, in toluene using a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex as the catalyst. The new crosslinkable polymers with alkyl cyanide and ethylene oxide groups as the pendent were synthesized by ring opening polymerization and characterized by GPC and 1H NMR. And then, the crosslinked solid polymer electrolyte was prepared by UV radiation curing. The conductivities of samples were measured by impedance spectroscopy using an indium–tin oxide (ITO) electrode. As the results, the maximum ionic conductivities of the polymer were 1.15 × 10−5 Scm−1 at 20°C and 1 × 10−4 Scm−1 at 60°C. The electrolyte was stable electrochemically to 5V versus Li+/Li at room temperature.