Electromagnetic shielding materials play a significant role in solving the increasing environmental problem of electromagnetic pollutions. The commonly used metal-based electromagnetic materials suffer from high density, poor corrosion resistance, and high processing cost. Polymer composites exhibit unique combined properties of lightweight, good shock absorption, and corrosion resistance. In this study, a novel high angle sensitive composite is fabricated by combining carbon fiber (CF) fabric with thermoplastic polyurethane elastomer (TPU). The effect of stacking angle of CF fabric on EMI shielding performance of composite is studied. When the stacking angle of CF fabric changed, the electromagnetic interference (EMI) shielding effectiveness (SE) of CF fabric/TPU composite can reach a maximum of 73 dB, and the tensile strength can reach 168 MPa. In addition, the composite has anisotropic conductivity, which is conductive along the plane direction and nonconductive along the thickness direction. Moreover, the CF fabric/TPU composite manifests exceptional EMI-SE/density/thickness value of 383 dB cm2 g−1, which is higher than most of current EMI shielding composites reported in literature. In summary, CF fabric/TPU composite is an excellent EMI shielding material that is lightweight, highly flexible, and mechanically robust, which can be applied to the field of aerospace and some intelligent electronic devices.