Miniaturization and high frequency are two key features of the next generation electronic devices, thus advanced electronic packaging materials with high thermal conductivity and excellent electromagnetic shielding performance (EMI SE) are highly expected. This work presents poly (vinylidene fluoride)@multi-wall carbon nanotube/boron nitride (PVDF@MWCNT/BN) composites with effective EMI SE and satisfactory insulation and thermal conductivity through a tailor-made segregated double network. PVDF@MWCNT composite micro spheres were fabricated as the thermal and electrical conductive micro-network, then another BN macro-network was further prepared to provide electrical insulation and further thermal conductivity enhancement. This so-called double segregated network of PVDF@MWCNT/BN composites shows a thermal conductivity of 0.83 W m(-1) K-1, electron insulation of 8.33 x 10(-14) S cm(-1) and electromagnetic shielding of 8.68 dB at 8.2 GHz when loaded 5 wt% MWCNT and 40 wt% BN. The study sheds new lights on the development of special functional materials and the PVDF@MWCNT/BN composites are highly promising as a future electronic packaging material.