In order to enhance the thermal conductivity of poly(dimethyl siloxane) (PDMS), boron nitride (BN) and carbon nanotubes (CNTs) were incorporated as the thermally conductive fillers. The amount of BN was increased from 0 to 100 phr (parts per hundred rubber) and the amount of CNTs was increased from 0 to 4 phr at a fixed amount of the boron nitride (100 phr). The thermal conductivity of the composites increased with an increasing concentration of BN, but the incorporation of CNTs had only a slight effect on the enhancement of thermal conductivity. Unexpectedly, the thermal degradation of the composites was accelerated by the addition of CNTs in 100 phr BN filled PDMS. Activation energy for thermal decomposition of the composites was calculated using the Horowitz-Metzger method. The curing behavior, electrical resistivity, and mechanical properties of PDMS filled with BN and CNTs were investigated.