Using pulsed laser deposition, a layer of LiNbO3(:Fe) film with a thickness of 180 nm was coated onto, porous Si (PS) stored in air for 1 year. A photoluminescence (PL) band enhanced about three times was observed at similar to 625 nm with a same peak position as that of the stored PS. It is revealed that a new PL excitation band occurs at similar to 363 nm, which is nearly equal to the fundamental optical absorption edge position of LiNbO3. The X-ray diffraction results disclose that the enhancement of the PL intensity is closely related to formation of a textured LiNbO3 film. Based on spectral analysis, we attribute the enhanced PL to optical transition in the E ' defect centers localized at the surfaces of PS nanocrystals, whereas the photoexcited carriers mainly come from the coated LiNbO3 film. This kind of LiNbO3(:Fe)/PS structures is expected to have important applications in modem ferroelectric optoelectronics. (c) 2004 Elsevier B.V. All rights reserved.