The popularity of portable and wearable flexible electronic devices, coupled with the rapid advancements in military field, requires electromagnetic interference (EMI) shielding materials with lightweight, thin, and flexible characteristics, which are incomparable for traditional EMI shielding materials. The film materials can fulfill the above requirements, making them among the most promising EMI shielding materials for next-generation electronic devices. Meticulously controlling structure of composite film materials while optimizing the electromagnetic parameters of the constructed components can effectively dissipate and transform electromagnetic wave energy. Herein, the review systematically outlines high-performance EMI shielding composite films through structural design strategies, including homogeneous structure, layered structure, and porous structure. The attenuation mechanism of EMI shielding materials and the evaluation (Schelkunoff theory and calculation theory) of EMI shielding performance are introduced in detail. Moreover, the effect of structure attributes and electromagnetic properties of composite films on the EMI shielding performance is analyzed, while summarizing design criteria and elucidating the relevant EMI shielding mechanism. Finally, the future challenges and potential application prospects of EMI shielding composite films are prospected. This review provides crucial guidance for the construction of advanced EMI shielding films tailored for highly customized and personalized electronic devices in the future.