Polymer composites with high thermal conductivity have recently attracted much attention, along with the rapid development of the electronic devices toward higher speed and performance. However, a common method to enhance polymer thermal conductivity through an addition of high thermally conductive fillers usually cannot provide an expected value, especially for composites requiring electrical insulation. Here, we show that polymeric composites with silver nanoparticle-deposited boron nitride nanosheets as fillers could effectively enhance the thermal conductivity of polymer, thanks to the bridging connections of silver nanoparticles among boron nitride nanosheets. The thermal conductivity of the composite is significantly increased from 1.63 W/m-K for the composite filled with the silver nanoparticle-deposited boron nitride nanosheets to 3.06 W/m-K at the boron nitride nanosheets loading of 25.1 vol %. In addition, the electrically insulating properties of the composite are well preserved. Fitting the measured thermal conductivity of epoxy composite with one physical model indicates that the composite with silver nanoparticle-deposited boron nitride nanosheets outperforms the one with boron nitride nanosheets, owning to the lower thermal contact resistance among boron nitride nanosheets’ interfaces. The finding sheds new light on enhancement of thermal conductivity of the polymeric composites which concurrently require the electrical insulation.