Using tetraethyl orthosilicate as a main raw material, silica nanofibers (SiNFs) were prepared through the combination of a sol-gel process and an electrospinning technique followed by pyrolysis. Surface modified electrospun SiNFs developed by self-polymerization of polydopamine on the surface (SiNFs-PDA) served as templates for the electroless plating of silver nanoparticles (Ag NPs), using glucose as a reducing agent. The electrical resistivity of silver coated SiNPs-PDA (SiNFs-PDA/Ag) was measured by the four-point probe method and was found to be as low as 0.02 m Omega.cm at room temperature. The morphology of SiNFs-PDA/Ag before and after the blending with silicon rubber indicated a strong interaction between the silver layer and the SiNFs-PDA. The electrical and mechanical properties of the silicon rubber filled with SiNFs-PDA/Ag were studied to demonstrate the conductive performance application of SiNFs-PDA/Ag.