We report on the surface morphology, crystalline, and electronic properties of Fe thin films potentiostatically eletrodeposited on hydrogen-terminated Si(111) substrates. Spontaneous reaction between Fe deposits and hydrogen-terminated Si surfaces have been observed at room temperature with formation of polycrystalline silicides Fe2Si and Fe5Si3, together with metallic Fe having a body-centered cubic structure. X-ray photoemission spectroscopy and X-ray diffraction measurements have been performed to investigate the thermal stability between Fe and Si under high-vacuum thermal treatments up to 300 degrees C.