Abstract: With the growing prevalence of electromagnetic contamination, the development of advanced electromagnetic shielding materials has emerged as critical research topic. This study proposes a synergistic electrospinning-electrospraying technique to fabricate a sandwich layered-structured nanocomposite film. Specifically, the top and bottom layers are made of lignin/polyacrylonitrile (PAN) electrospun nanofibers, while the intermediate layer is engineered via the synergistic electrospinning-electrospraying process to uniformly deposit MXene onto the surface of nanofibers. Notably, due to the self-deposition of MXene, the intermediate layer exhibits a MXene-dominated conductive layered structure, facilitating multiple reflections and absorptions of electromagnetic waves. The results demonstrate that the film achieves an EMI shielding effectiveness of 44.1 dB at a low MXene loading of 15 wt.%, featuring with superior electromagnetic shielding efficiency under relatively low conductive filler dosage. Furthermore, the electromagnetic shielding effectiveness increases to 72.9 dB when 4 layers of the film is piled up. Furthermore, the sandwich structure effectively protects MXene, which significantly improved the stability and durability of the materials. This work provides a novel strategy to design high-performance, lightweight, and flexible electromagnetic shielding materials.