Abstract Single-phase β-FeSi2 films were fabricated on silicon (100) substrates by pulsed laser deposition (PLD) technique and post-annealing process. The X-ray diffraction (XRD) showed that the diffraction intensity reached a certain threshold and then decreased with the increase of annealing time. The scanning electron microscopy (SEM) observations revealed surface morphologies of the films for different annealing times. The optimal photoluminescence (PL) of the films was obtained after 9 h annealing process. Based upon all the experimental results, it was found that the luminous properties were associated with the crystalline quality and surface morphologies.