This study focuses on the characterization of iron silicide grown, for the first time, by pulsed laser deposition on Si(111). Silicide growth was attempted both by deposition of pure Fe followed by annealing, and congruent deposition of Fe and Si from a stoichiometric FeSi2 target. The films formed by deposition of pure Fe and annealing did not grow epitaxially on Si(111) and contained a number of phases including β-FeSi2. Films grown by congruent deposition of Fe and Si did grow epitaxially on Si(111) and contained either pure β-FeSi2 or a mixture of both FeSi and β-FeSi2, depending on deposition conditions. The following epitaxial orientations were observed: β-FeSi2(001)//Si(111), β-FeSi2//Si<110> with three variants, and FeSi(111)//Si(111), FeSi//Sit[112^. Films of various thicknesses were analyzed with conventional transmission electron diffraction and microscopy.