We prepared β-FeSi2 thin-films by using a Pulsed Laser Deposition (PLD) method and succeeded to observe photoluminescence (PL) around 1.5 μm corresponding to β-FeSi2 band from the long-time and high-temperature annealed β-FeSi2 thin-films. The β-FeSi2 thin-films were ablated on Si(111) substrates heated at 550°C. After ablation, long-time and high-temperature thermal annealing was performed in order to improve the crystal-quality. Annealing times were 5, 10, 20 and 40 hrs, and annealing temperature was kept at 900 °C. Crystallinity was evaluated by an X-ray diffraction (XRD) measurement. We have observed eminent improvement on crystal-quality of β-FeSi2 thin-films. Annealed samples show (220) or (202) X-ray diffraction signals of β-FeSi2 and the full width at half maximum (FWHM) of these peaks were 0.27° although the thickness of the samples decreased with annealing time. Thermal-diffusion of Si atoms was observed from substrate to thin-films. Fe atoms in the ablated thin-films also diffused into the substrate. The relationship between the thickness of β-FeSi2 thin-films and the thermal-diffusion were investigated with rutherford backscattering (RBS) measurement. Maximum photoluminescence intensity around 1.5 μm was observed from the thickest β-FeSi2 thin-film with only 5 hrs annealing.