This study introduces a novel strategy based on metal-organic decomposition (MOD) to enhance the tube-tube interactions of carbon nanotubes (CNTs) in CNT films, leading to improved mechanical strength and ultra-broadband electromagnetic interference (EMI) shielding performance. The Ag particles are introduced in situ into the CNT film through annealing of MOD, resulting in enhanced tube-tube interactions. The Ag–CNT film exhibits an electrical conductivity of up to 6.82 × 10^5 S m^-1 and an EMI shielding effectiveness of over 66 dB in the ultra-broad frequency range (3–40 GHz). The tensile strength and Young’s modulus of the Ag–CNT film increase significantly, from 30.09 ± 3.14 MPa to 76.06 ± 6.20 MPa and from 1.12 ± 0.33 GPa to 8.90 ± 0.97 GPa, respectively. The Ag–CNT film also demonstrates excellent near-field shielding performance, effectively blocking wireless power transmission. This innovative approach provides an effective route to produce high-quality flexible shielding materials, which is critical for the development of portable and wearable electronic devices.This study introduces a novel strategy based on metal-organic decomposition (MOD) to enhance the tube-tube interactions of carbon nanotubes (CNTs) in CNT films, leading to improved mechanical strength and ultra-broadband electromagnetic interference (EMI) shielding performance. The Ag particles are introduced in situ into the CNT film through annealing of MOD, resulting in enhanced tube-tube interactions. The Ag–CNT film exhibits an electrical conductivity of up to 6.82 × 10^5 S m^-1 and an EMI shielding effectiveness of over 66 dB in the ultra-broad frequency range (3–40 GHz). The tensile strength and Young’s modulus of the Ag–CNT film increase significantly, from 30.09 ± 3.14 MPa to 76.06 ± 6.20 MPa and from 1.12 ± 0.33 GPa to 8.90 ± 0.97 GPa, respectively. The Ag–CNT film also demonstrates excellent near-field shielding performance, effectively blocking wireless power transmission. This innovative approach provides an effective route to produce high-quality flexible shielding materials, which is critical for the development of portable and wearable electronic devices.