Porous silicon (PSI) samples with high photoluminescence (PL) efficiency were examined using microscopic mapping techniques including scanning electron microscopy (SEM) and spatially resolved photoluminescence (SRPL). Studies of the growth conditions indicate that the homogeneity of the PL and the surface roughness of the sample depend on the preparation procedure of the PSI layer. SEM and spatially-resolved reflectance scans of an n-type sample with a PSI layer on the order of 100 μm reveal a highly fractured surface. SRPL of the same sample shows non uniform PL on a scale of 5 μm. Cross-sectional analysis of the samples with SRPL and SEM reveals the intricate multilayer structure of the PSI film. The top portion of the PSI film is largely responsible for the PL and is composed of isolated column-like structures. We have also observed cross-shaped structures reminiscent of stress fractures on the surface of PSI films using SEM or optical microscopy. Furthermore, atomic force microscopy (AFM) and SEM measurements of the surface of PSI films of intermediate thickness reveal that samples which appear smooth on approximately 1 μm scale are actually covered with clumped structures on the order of 100 to 150 nm.