We have developed a new, minimal damage approach for examination of luminescent porous Si layers (PSLs) by transmission electron microscopy (TEM). In this approach, chemically etched PSLs are fabricated after conventional plan-view TEM sample preparation. A diffraction pattern consisting of a diffuse center spot, characteristic of amorphous material, is primarily observed. However, crystalline, microcrystalline, and amorphous regions could all be observed in selected areas. A crystalline mesh structure could be observed in some of the thin areas near the pinhole. The microcrystallite sizes were 15–150 Å and decreased in size when located further from the pinhole.