We have made structural and compositional studies of luminescent laterally anodized porous Si. Scanning electron microscopy reveals a surface with a network of cracks, while transmission electron microscopy shows a dual porous Si structure in which the upper layer is amorphous and the lower layer is either amorphous or crystalline, depending on anodization conditions. X-ray diffraction verified the presence of the amorphous layer. Secondary ion mass spectroscopy reveals very high concentrations of H, B, C, N, O, and F in the amorphous layer. Our results indirectly suggest that the amorphous layer is primarily responsible for luminescence.