With the rapid development of portable electronics, the demand for flexible shielding and thermal management materials is increasing steadily. Herein, we reported a scalable flexible graphene film preapred following hydrogen iodide chemical reducing and graphitization thermal reducing. Benifitting from the coordinated reduction, the fabricated graphene film is equipped with varous characteristics of high orientation, rich defect and three-dimensional porosity. Then the graphene film deliver outstanding mechanical property and electrical conductivity (1.2 × 105 S m−1). Moreover, superior electromagnetic interference (EMI) and thermal conductivity are realized compared with the simplex thermal reduction. The EMI effectiveness can reach a high value of 70 dB when the thickness is only 35 μm, and the specific EMI effectiveness is 380 dB/g cm−3. And the relationship between the effectiveness and structure parameters (thickness and density) is uncovered. The thermal conductivity could be up to 864 W m−1 K−1. This research may not only provide a new avenue to the development of flexible shielding and thermal management materials, but also promote the application of graphene.