α,ω-Hydrogen polyorganosiloxane (HPMDMS) prepolymer was prepared from equilibrium polymerization of octamethylcyclotetrasiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, and 1,1,3,3-tetramethyl disiloxane as an end-blocker in the presence of tetramethylammonium siloxanolate as a catalyst. Polyorganosiloxane modified with dimethylacrylamide (APMDMS) was prepared by hydroxilylation of HPMDMS with dimethylacrylamide in the presence of Pt catalyst, and followed by coordination of metal oxide (APMDMS-MO), such as NiO and FeO, to the amide moieties of the resulting polymer. The chemical structures of HPMDMS and APMDMS were confirmed by FT-IR and ¹H-NMR analysis. Liquid silicone rubber containing metal oxide composite (LSRMO) was prepared by compounding APMDMS-MO, α,ω-vinylpolydimethylsiloxane, and a catalyst in a high speed dissolver. The thermal conductivity of LSRMO composite was determined to be 0.29 W/mK, and the volume resistivity exhibited a lower value than that of LSR composite. The mechanical and thermal properties of LSRMO and LSR composite were measured by UTM and TGA.