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Compound semiconducting silicide -FeSi 2 has been formed on FZ -Si (111) substrates by means of pulsed laser deposition (PLD) method using ArF ( = 193 nm) excimer laser. In photoluminescence (PL) measurements at 8K detected by a Ge detector, the PL spectra of the samples annealed at 900 C for 1, 5, 8 and 20 hrs showed that the PL intensities of the A-and peak increased depending on annealing time in comparison with those of the as-deposited sample. The intrinsic PL intensity of the A-band peak from 20 hr annealed sample was investigated. The dependence of the PL excitation power density of the 20-hr-annealed sample also showed A-band peak at 0.808 eV that almost constant peak position. The temperature dependence PL intensity of the 20-hr-annealed sample in the ranges 15K~150K by an InGaAs detector showed the PL peak was at 0.808 eV. This peak confirmed the intrinsic PL peak of A-band of theFeSi 2 . The transmittance of the thin films was measured in the range 0-2500 nm. Moreover, it is calculated the refractive indices using the reflectance. We report an application ofFeSi 2 with crystalline and luminescence characteristics with a high refractive index in photonics.