High-performance multifunctional EMI shielding composite fabricated by low-cost method is increasingly required. Herein, novel EMI shielding nanocomposite laminates, consisting of composite prepreg of carbon fiber/epoxy resin/carbon nanotube film, were manufactured by facile electric heating of carbon nanotube film. The results indicated that composite with excellent specific shielding effectiveness of 0.07 dB/μm, 47 dB cm³/g and metamaterial properties can be designed by composite prepreg, and the primary shielding mechanism of it was reflection loss, along with interface polarization loss and conductive loss, which was superior to lots of shielding materials including carbon nanotube-based, carbon black-based, carbon nanofiber-based and graphene-based materials reported previously. Meanwhile, highly required excellent properties, including the thermostability with initial decomposition temperature up to 300 °C, hydrophobicity over contact angle of 115°, corrosion resistance of the composite with metal-free modification, and function as structural laminate compared with previous studies were demonstrated, which suggested tremendous potentials of the multifunctional EMI shielding composites in harsh environment.