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The self-made hollow porous micro/nano-fiber structure Sn_0.84Sb_0.08Sm_0.08O₂ and thermoplastic polyurethane (TPU) were used as raw materials to prepare the Sn_0.84Sb_0.08Sm_0.08O₂/TPU (the addition content of Sn_0.84Sb_0.08Sm_0.08O₂ is 0wt%, 3wt%, 6wt%, and 9wt%) composite micro/nano-fiber films by electrostatic spinning method. Results show that the microstructures of composite films all present a fibrous 3D network structure. The tensile strength and elongation of the composite film are increased firstly and then decreased with increasing the addition content. When the addition amount is 6wt%, the tensile strength and elongation of the film are 2.68 MPa and 573%, which are 1.5 and 8.3 times higher than those of TPU film, respectively. The addition of Sn_0.84Sb_0.08Sm_0.08O₂ increases the thermal decomposition temperature and contact angle of the composite films to 303 °C and 120°, respectively. The infrared emissivity of the composite film is decreased with increasing the filler content. When the addition content is 9wt%, the infrared emissivity of the specimens at wavelength of 3–5 and 8–14 μm is 0.576 and 0.652, respectively. This composite film has good hydrophobicity, thermal stability, flexibility, and infrared stealth performance, providing experimental basis for the research of lightweight infrared stealth materials and showing certain application potential in the infrared stealth field.