Multilayer graphene/polymer composite films with good mechanical flexibility were fabricated into paraffin-based sandwich structures to evaluate electromagnetic interference (EMI) shielding. Experimental results showed the relationship between electrical properties and shielding performance, demonstrating that electrical properties are significant factors in EMI shielding. Calculation based on electrical conductivity of the composite films was carried out to investigate the fundamental mechanisms of absorption, reflection and multiple-reflections for the polymeric graphene composite films. Both experimental and calculated results indicate that reflection is the dominating shielding mechanism for the as-fabricated polymeric graphene films. The optimization of thickness, skin depth and electrical conductivity in the shielding materials could be highly significant in achieving enhanced EMI shielding. Further improvement in absorption shielding has been achieved by increasing the shielding thickness in order to enhance the overall shielding performance. The optimized shielding effectiveness up to 27dB suggested effective shielding of the composite films. The implication of the mechanisms for optimizing shielding performance demonstrates significant fundamental basis for designing high-performance EMI shielding composites. The results and techniques also promise a simple and effective approach to achieve light-weight graphene-based composite films for application potentials in EMI shielding coatings.