A flexible and multi-layered graphene nanosheets (GNSs)-Fe₃O₄/poly (vinylidene fluoride) hybrid composite film with high-efficient electromagnetic interference (EMI) shielding was fabricated via a facile layer-by-layer coating. The well-designed multi-layered and hybrid electromagnetic fillers endow the prepared film with good surface impedance matching and prominent internal multiple absorption, which forms “absorb-reflect-reabsorb” electromagnetic transmission pattern and results in highly efficient electromagnetic shielding effectiveness (EMI SE). The resultant composite film exhibits an exceptional EMI SE of 52.0 dB at a thickness of 0.3 mm. What is more important is that the prepared film exhibits excellent flexibility and EMI stability, and the retention rate of efficient EMI SE is high as 91.9% after 1000 bending-release cycles. This study provides a feasible strategy for designing high-efficient EMI shielding film with excellent flexibility and ultra-thin thickness that suitable for next-generation intelligent protection devices.