High-performance electromagnetic interference (EMI) shielding materials possess features of light weight, flexibility and excellent EMI shielding effectiveness. However, continuous efforts are still needed to satisfy the urgent demand for electromagnetic pollution shielding. In this study, a lightweight and flexible hybrid film with a multi-scale double-continuous conductive network (TiO2/SiO2@PPy) and sandwich structure (TiO2/SiO2@PPy@rGO) was prepared via a delicate structure design of electrospun TiO2/SiO2 nanofibers. The hybrid film worked as an effective dissipative medium, leading to a high EMI shielding effectiveness of approximately 30 dB in the X band (8-12 GHz) and excellent specific EMI shielding effectiveness (SE) of ∼13 829 dB cm2 g-1. The hybrid film has a tensile strength of 2.71 MPa, while its density is only 0.089 g cm-3. The hybrid films maintained good electrical and EMI shielding properties after repeated bending, indicating their favorable flexibility. The delicate structure-design strategy of the electrospun nanofibers presents a practicable way to prepare lightweight and flexible hybrid films for high-performance EMI shielding materials in flexible electronics, military and healthcare applications.