Gaining brilliant flexible, easily-processable, bendable, low-density and high electrical conductivity (σ) materials with an excellent electromagnetic-interference (EMI) shielding performance is urgently needed in the fields of aerospace, aircraft, military, wearable and portable electronic industries. Therefore, the growing desire towards miniaturizing and developing high-frequency electronics is increasing incredibly today and grabbing much attention, however, they cause extreme heat accumulation and EM radiations that affect their performances as well as their hazardous effects on human health. So, polymer nanocomposites with high thermal conductivity (k) and EMI shielding effectiveness (SE) synchronously are urgently required to consume the generated heat and blocks the EM waves. Herein, poly(vinyl alcohol)/graphene nanosheets/carbonyl iron (PVA/GRx/CIR0.1-x) nanocomposite films are introduced as a new alternative candidate for EMI shielding applications with high in-plane k//, high mechanical functions, and EMI SET performance. The synergistic effect of GR and CIR on EMI shielding functions, thermal stability, mechanical properties, electrical features, and surface morphology has been explored. The increase in GR(x) amounts provides continuous GR layers and dense networks for conducting electrons and heats, provides the films with an admirable k// and total SE (SET) synchronously. Particularly, the PVA/GR0.08/CIR0.02 films have shown an σ of 1.72 Sm−1, a large SET of 32.94 dB and a specific SE (SSE/t) of 4365 dBcm2g−1 due to the mutual role (effect) of both high electrical conductive graphene and high magnetic carbonyl iron in cancelling the magnetic and electric fields of the incident EM waves. Moreover, the layered structure of GR endows films with a high k// of 3.62±0.11 W/(m·K), which is 14-fold larger than that of green PVA. The high compatibility and fine dispersion of GR/CIR fillers endow the films with a high Young modulus of 2.16 GPa, which is 7-fold larger than that of green PVA. This work suggests a novel and feasible scheme for producing high EMI shielding and high thermal conductive polymeric films, which will have huge prospects in advanced technology such as electromagnetic (microwave) interference shielding, wearable, biological, smart fabrics, military technologies and electronic equipments.