We present the investigation on LaF₃/porous silicon (PS) system that has properties of both the materials to be applied in photonics. Epilayers of LaF₃ are grown on PS under different anodization conditions using electron-beam evaporation (EBE). The characteristics of the LaF₃/PS system are analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and photoluminescence (PL). XRD confirms the polycrystalline nature of the LaF₃ film. Nearly stoichiometric growth of LaF₃ on PS is established by EDX. Such a thin LaF₃ layer grown on PS leads to a good enhancement of PL yield of PS. But with the increasing thickness of LaF₃ layer, PL intensity of PS is found to decrease along with a small blue-shift.