Polycrystalline silicon thin films may be used to prepare luminescent porous silicon for optoelectronic devices. Photoiuminescence properties and in depth structure of porous-Si films obtained from n+ poly-Si are studied as a function of electrochemical etching under illumination. The effect of grain boundaries on the homogeneity of porous-poly-Si films and on the formation of macropores in the substrate were shown using scanning and transmission electron microscopy (SEM and TEM).