Here, we study the self-aligned asymmetrical ectrically conductive composite thin film prepared via casting of graphene oxide (GO)/poly (vinylidene-hexafluoropropylene) (PVDF-HFP) dispersion, followed by low temperature hydriodic acid reduction. The results showed that composite thin film revealed the high orientation of graphen esheets along the direction of film surface. However, graphene sheets are asymmetrically distributed along the film thickness direction in the composite film. Both sides of as prepared composite film showed different surface characteristics. The asymmetric surface properties of composite film induced distinction of surface resistivity response; top surface resistivity (21Ohm) is ∼ 4 times higher than bottom surface resistivity (5Ohm). This asymmetric highly electrically conducting composite film revealed efficient electromagnetic interference (EMI) shielding effectiveness of ∼ 30 dB. This study could be crucial for achieving aligned asymmetric composite thin film for high-performance EMI shielding radiation.