In the microwave region, graphene material usually has a relatively high resistivity, which limits its application potential in electromagnetic shielding and radiation. Meanwhile, conventional carbon materials are difficult to meet the requirement of electronic devices and electromagnetic shielding in terms of thickness reduction and flexibility. Here, a flexible multilayer graphene film (MGF) with high conductivity and small thickness is achieved by high temperature thermal treatment of GO films and subsequence compression rolling. We experimentally study the EMI shielding performance of the MGF with a thickness of 27 μm, which shows high shielding effectiveness (SE) of 70 dB from 2.6 GHz to 40 GHz. Making use of its high conductivity of 1.13 × 106 S/m and low sheet resistance of 32.7 mΩ/□, a MGF based multi-beam millimeter wave antenna array with average gain of 15.07 dBi and large beam scanning range of 120°is realized for the first time. All the measurements indicate that the flexible, low thickness, low-density and highly conductive multi-layer graphene film have great potential in the application of electromagnetic shielding, electromagnetic conduction and electromagnetic radiation devices.