Sn_1-xSm_xO₂ (x=0wt%, 8wt%, 16wt%, 24wt%) micro/nano-fibers were prepared by electrospinning combined with heat treatment. The phase, morphology, infrared emissivity, and laser absorption properties of the products were characterized. The first principles simulation based on density functional theory was used to compare and analyze the photoelectric properties of Sn_1-xSm_xO₂ (x=0wt%, 16wt%) material, and the effect mechanism of Sm³⁺ doping on the infrared emissivity and laser absorption of SnO₂ from the perspective of electronic structure was further clarified. Results show that after calcination at 600 °C, the calcined Sn_1-xSm_xO₂ micro/nano-fibers all present the single rutile structure and show good fiber morphology. The fibers interlace with each other, forming irregular three-dimensional network structure, and the elements are evenly distributed on the fiber. With increasing the Sm³⁺ doping amount, the reflectivity of Sn_1-xSm_xO₂ micro/nano-fibers is decreased gradually at wavelength of 1.06 and 1.55 μm, and the infrared emission is decreased firstly and then increased. When x=16wt%, the reflectivity at wavelength of 1064 nm is 53.9%, the reflectivity at wavelength of 1550 nm is 38.5%, and the infrared emissivity at wave band of 8?14 μm is 0.749, which provides a theoretical and practical basis for the thin, light, wide-band, and high-performance laser-infrared compatible stealth materials.