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In order to improve electrical conductivity of electronic packaging materials, we synthesize 4'-allyloxy-biphenyl-4-ol (AOBPO) and use the AOBPO functionalized MWCNTs (A-MWCNTs) as fillers mixed with silicone resin to fabricate nanocomposites. The electrical and mechanical performances of the nanocomposites were investigated by using dynamic mechanical analysis (DMA) and integrated electrochemical analyzer. The results show that AOBPO can disperse carbon nanotubes via π-π interactions and has good compatibility with the silicone resin matrix. the A-MWCNTs/silicon resin nanocomposites has a higher electrical conductivity than the unfunctionalized MWCNTs(U-MWCNTs)/silicon resin nanocomposites, and A-MWCNTs/silicone resin nanocomposites has a lower storage modulus than the U-MWCNTs/silicon resin nanocomposites, These results prove the effect of functionalization of MWCNTs with AOBPO on the interfacial adhesion and dispersion between silicon resin and MWCNTs, Which is further confirmed by morphology study of fractured surfaces of nanocomposites by SEM.