Bifunctional materials with electromagnetic shielding and thermal conductivity are becoming more and more popular as a solution to the problems of heat dissipation and heat transfer brought on by the rapid development of communication and electronic equipment. However, investigations on such bifunctional materials are rare. Herein, a three-dimensional network of graphene (TPU/G) was effectively created by utilizing sodium chloride (NaCl) as the template and thermoplastic polyurethane (TPU) as the binder. A further carbonization process was employed to generate the C/G network, which was subsequently encapsulated in epoxy resin. The composites exhibit pretty electromagnetic interference shielding effectiveness (EMI SE) as well as thermal conductivity thanks to the three-dimensional graphene network design. When the graphene loading is 4.14 wt%, the combination of electromagnetic shielding effectiveness and thermal conductivity reaches its optimum. And at this time, the EMI SE can reach 35.23 dB, and the thermal conductivity is 1.19 W m⁻¹ K⁻¹. The prepared composites have broad potential applications in the fields of electromagnetic shielding and thermal management.