In this paper, (3-mercaptopropyl)trimethoxysilane (MPTS)- and copper-coated carbon fiber (M-Cu-CF) was obtained by electroless plating method. The M-Cu-CF was evaluated by FTIR, XRD, TGA, and SEM. It was found that the MPTS and Cu were coated on the fiber surface successfully. The M-Cu-CF was utilized as a conductive filler in silicone rubber (SR) for thermal and electrical conductivity applications and exhibited good dispersion and compatibility with the matrix. The effect of M-Cu-CF content on the thermal conductivity and volume resistivity of silicone rubber composites was investigated. The results showed that the thermal conductivity of the M-Cu-CF/SR composites reached 1.99 W (m K)(-1) with only 4.0 wt% filler loading, approximately 2.10 times higher than that of raw-CF/SR composites at the same loading. And with the increase of M-Cu-CF loading, the least volume resistivity of M-Cu-CF/SR composites was 3.5 x 10(3) Omega cm.