The structural design of thin films is attracting attention in academia and industry in attempts to improve electromagnetic interference shielding effectiveness (EMI SE). In this study, MXene/chitosan/silver nanowire (AgNW) sandwich films, in which the AgNW core layer was bordered by two MXene/chitosan layers, were fabricated by vacuum-assisted filtration. Because of the interconnected AgNWs in the core layer and the aligned MXene sheets in the MXene/chitosan layers, the electrical conductivity of the sandwich film reached 11,459.1 S/m. Consequently, the sandwich film exhibited an SE value of 82.3 dB. What is more, when both the AgNW and MXene contents were 33.3%, the sandwich film’s EMI SE divided by its thickness was 26,167 dB/cm, which was much superior to the values reported for inorganic hybrid composites and polymer composites filled with hybrid fillers. Such a simple approach was proved to be an effective way for further structure design of thin films in EMI shielding field.